EP3794167B1 - Nettoyage des râteliers dans un procédé de dépôt électrophoréctique - Google Patents

Nettoyage des râteliers dans un procédé de dépôt électrophoréctique Download PDF

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Publication number
EP3794167B1
EP3794167B1 EP19720648.5A EP19720648A EP3794167B1 EP 3794167 B1 EP3794167 B1 EP 3794167B1 EP 19720648 A EP19720648 A EP 19720648A EP 3794167 B1 EP3794167 B1 EP 3794167B1
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EP
European Patent Office
Prior art keywords
cleaning
aqueous
coating
component
agent
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EP19720648.5A
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German (de)
English (en)
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EP3794167A1 (fr
Inventor
Jan-Willem Brouwer
Jens Kroemer
Frank-Oliver Pilarek
Fernando Jose RESANO ARTALEJO
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment
    • 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
    • C23C22/07—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 phosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/19—Iron or steel
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes

Definitions

  • the present invention relates to a method for the anti-corrosion coating of metallic components in series, comprising several wet-chemical treatment stages including a cathodic electro-dip coating, which concludes the coating process, in which each component is picked up by a conveyor frame and the transport pair consisting of component and conveyor frame is then guided through all treatment stages before the finished coated component is separated from the conveyor and an uncoated component is picked up by the same conveyor for coating, the process preventing the build-up of massive paint deposits on the conveyors by incorporating an additional treatment step before cleaning/degreasing and subsequent passivation and electrocoating .
  • the coating process in the method according to the invention can be operated economically from pretreatment to electrocoating in a single system (so-called "single loop"), since the ejection of individual conveyor elements for removing paint deposits after the integration of precleaning is no longer necessary.
  • An effective removal of the paint components taken on the conveyor frames from the cathodic electrocoating succeeds within the scope of the present invention by merely bringing the conveyor frames and thus also the components to be coated on the conveyor frame into contact with an aqueous agent of suitable acidity containing phosphoric acid before the wet-chemical treatment stages for cleaning/degreasing, passivation and cathodic electrocoating.
  • the anti-corrosion pretreatment of metallic components in particular consisting of the materials zinc, iron, steel, galvanized steel and/or aluminum, in a process sequence comprising a passivation, e.g. based on water-soluble phosphates or based on water-soluble compounds of the elements Zr, Ti and/or or Si, followed by electrocoating has been established or known in principle in the prior art for decades.
  • the passivation can involve the formation of a crystalline conversion layer, for example a phosphate layer corresponding to the EP2503025 or just the formation of an amorphous coating, for example.
  • a zirconium phosphating according to the EP2215285 , effect.
  • Coating in a single system is advantageous in terms of process technology, in which a transport pair consisting of conveyor frames together with the body is guided through all treatment stages including electrocoating, the body is then separated from the conveyor frame and discharged for the baking stage, which provides for the drying, filming and curing of the electrocoating and the conveyor frame, freed from the body, picks up an untreated and therefore uncoated body in order to go through the coating process again (so-called "single-loop system").
  • Each conveyor frame of such a single-loop system thus runs through all wet-chemical treatment stages as often as is necessary to coat the specified series of bodies with a corrosion-protective coating, or as often as possible before maintenance of the system becomes necessary.
  • the profitability of a single-loop system is therefore, despite its fundamentally efficient mode of operation due to the required regular maintenance of the conveyor frames and the associated system downtime, compared to production lines in which the body is separated from its conveyor frame after passivation and before electrocoating and for further coating of a second conveyor frame system is often not given.
  • the object of the present invention is therefore to improve the profitability of a single-loop system for the anti-corrosion coating of metallic components in series, including their cleaning/degreasing, passivation and cathodic electrocoating, by ensuring continuous operation of the coating system during series production.
  • This object is achieved in a process for the anti-corrosion coating of metallic components in series, comprising at least cleaning/degreasing, passivation and cathodic electrocoating, each as a wet-chemical treatment stage, with the cleaning/degreasing treatment stage always being that of passivation in the process sequence for the anti-corrosion coating and is based on an aqueous cleaning solution with a pH above 6, and the treatment stage of cathodic electrocoating always follows that of passivation in the process sequence for anti-corrosion coating, in which each component of the series to be pretreated is picked up by a conveyor frame, then the transport pair consisting of component and conveyor frame is guided through the wet-chemical treatment stages according to the process sequence and the transport pair separates only after the last treatment stage r separated and a anti-corrosion coated component is ejected, and then the conveyor frame released in this way picks up a next component of the series in order to run through the process sequence again for the purpose of the corrosion-protective coating of the same, the conveyor frame
  • a metallic component within the meaning of the present invention is present if the component is at least partially composed of at least one metallic material, preferably zinc, iron, aluminum and the respective alloys, insofar as the aforementioned elements each contain the main alloy component with more than 50 at. -% form, as well as galvanized steel.
  • An anti-corrosion coating in series according to the present invention is present when a large number of metallic components pass through the wet-chemical treatment stages, with the coating of each component taking place one after the other and thus at different times.
  • a process sequence for anti-corrosion coating comprises a predetermined sequence of wet-chemical treatment stages from the picking up of the component to be coated by the conveyor frame to the removal of the now-coated component for the purpose of transfer to subsequent treatment stages, e.g. the baking stage, with each individual wet-chemical treatment stage provides for the component and at least parts of the conveyor frame to be brought into contact with an aqueous medium.
  • a conveyor frame is any device suitable for receiving, transporting and ejecting the component, the suitability also consisting in being able to guide the component through the spatially separated wet-chemical treatment stages according to the process sequence according to the invention and doing so as little as possible To deliver material to the treatment stages as well as to receive material from the treatment stages.
  • Conveyor frames are therefore preferably made of materials that are inert to the media applied in the treatment stages, for example stainless steel, and have an external design that minimizes the scooping of media from the respective treatment stage into the respective subsequent one.
  • a transport pair is implemented within the scope of the present invention, namely until the component is transferred to a next system, in particular a conveyor frame system, e.g. for baking the electrophoretic paint, for further treatment outside the process sequence according to the invention for anti-corrosion coating so that it is ejected.
  • the conveying frame is released again as soon as the metallic component with a corrosion-protection coating according to the process sequence has been discharged and can receive another metallic component to be coated with a corrosion-protection coating.
  • a large number of conveying frames are also used for the quasi-continuous treatment of a large number of components in series; the number of conveying frames preferably corresponds at least to the number of wet-chemical treatment stages.
  • the total acid content in points is determined within the scope of the present invention by diluting 10 ml of the aqueous pre-cleaning agent to 50 ml and titrating with 0.1 N sodium hydroxide solution to a pH value of 8.5.
  • the consumption of milliliters of caustic soda indicates the number of points for the total acidity.
  • the pH value corresponds to the negative decade logarithm of the activity of the hydronium ions measured using pH-sensitive glass electrodes at 20 °C after they have been calibrated with pH buffer solutions suitable for the relevant pH value range.
  • each conveyor frame is, after receiving the next component to be coated, passed through all the treatment stages required for the coating in the pre-cleaning of Effectively removes binder and pigment residues.
  • the pre-cleaning is matched to the type of electrocoating and requires an acidic aqueous agent for detaching cathodic dip-coating residues from the conveyor frames in the pre-cleaning.
  • Electrocoating in the sense of the present invention characterizes a wet-chemical treatment stage, during which a hardenable paint coagulum is deposited on the metallic component by applying an electrical voltage, which is filmed and hardened in a subsequent treatment stage by baking.
  • the electrocoating is preferably based on an aqueous medium containing at least one dispersed organic resin in an amount of at least 1% by weight based on the aqueous medium.
  • the electrophoretic coating can be deposited cathophoretically, ie by applying an electrical voltage at which the metallic component to be coated to protect against corrosion is connected as a cathode.
  • cathodic electrocoating in which an alkaline pH shift at the interface to the metallic component causes the coagulation of the dispersed resin particles and thus the formation of a layer on the component.
  • Cathodic electrocoating is established in particular for the anti-corrosion coating of passivated, e.g. zinc-phosphated or coated with amorphous conversion layers metallic components and is used as standard in the coating of automobile bodies.
  • An epoxy resin is preferably used as the binder, which in turn is preferably selected from amine-modified polyepoxides, for the cathodic dip coating, the dip coating to be applied cathodically preferably additionally containing blocked and/or unblocked isocyanate groups containing organic compounds as hardeners and particularly preferred additionally also includes at least one water-soluble compound of the element bismuth and/or the element yttrium, each of which is capable of exerting a positive influence on the crosslinking of the paint coagulum in the baking stage.
  • Water-soluble if its solubility in deionised water with a conductivity of not more than 1 ⁇ Scm -1 at a temperature of 20 °C is at least 1 g/kg.
  • the coagulation tendency of paint residues of cathodic dip paints in alkaline media causes the formation of massive paint deposits and incrustations on conveyor frames, which run through the process sequence for anti-corrosion coating of the series of metallic components based on cathodic electro-dip painting in single-loop operation, and this especially when the After picking up the next component to be coated for protection against corrosion, the conveyor frames that have been driven out of the dip coating first enter the cleaning/degreasing treatment stage, which is usually based on a neutral cleaning agent or an alkaline cleaning agent.
  • the establishment of a method according to the invention for the economy of a single-loop system comprises a conventional process sequence consisting of cleaning / degreasing based on an aqueous cleaning solution with a pH value above 6, passivation and cathodic electrocoating, in which the treatment stage of passivation cleaning/degreasing as a wet-chemical treatment stage within the process sequence for the anti-corrosion coating of components in series, which in turn follows the treatment stage of pre-cleaning, is essential.
  • the aqueous cleaning solution for cleaning/degreasing is preferably alkaline and particularly preferably has a pH above 8, particularly preferably a pH above 10.
  • the cleaning/degreasing based on the aqueous cleaning solution follows the pre-cleaning, preferably without an intermediate rinsing step and without a drying step.
  • directly means without one or more intermediate wet-chemical treatment steps that do not represent rinsing steps.
  • the aqueous agent in the pre-cleaning has a total acid content of at least 3 points.
  • the total acid content of the acidic aqueous precleaning agent is preferably at least 5 points, more preferably at least 10 points and particularly preferably at least 20 points.
  • a pH of the aqueous agent in the pre-cleaning of less than 5.5 is preferred, particularly preferably a pH of less than 5.0 and particularly preferably a pH of less than 4.5.
  • the pH of the aqueous agent in the pre-cleaning is not less than 2.0, particularly preferably not less than 2.5. If a pH value of the aqueous medium of less than 2.5 is required for the effective removal of dipping paint residues on the conveyor frames, it is therefore advantageous if corrosion inhibitors known to the person skilled in the art are added.
  • a certain buffer capacity in the pre-cleaning has proven to be advantageous in order to maintain a good separation performance with regard to the dip paint residues from the conveyor frames, so that in processes with cathodic electro-dip painting, preferably those acids are used to adjust the total acidity of the aqueous medium in the pre-cleaning, whose pKa value is above 2.5 but below 5.5.
  • the proportion of acids with a pKa value in the preferred range of 2.5-5.5 contributes at least 80% to the total acid content.
  • Suitable representatives of such acids are phosphoric acid, which is obligatory anyway, but also phosphoric acid esters, organic diphosphonic acids, ⁇ -hydroxycarboxylic acids and mono- and dicarboxylic acids, such as gluconic acid, acetic acid, citric acid or tartaric acid.
  • Suitable acids whose pKa value is not above 2.5 and which can also be used to adjust the total acidity of the aqueous precleaning agent are nitric acid, sulfuric acid, ethylenediaminetetraacetic acid, etidronic acid and amidosulfonic acid.
  • the passivation downstream of the pre-cleaning is a phosphating or if the pre-cleaning in such processes is followed by cleaning/degreasing containing phosphates as builder substances
  • the provision of the total acid according to the invention in the aqueous medium of the pre-cleaning is based on the according to the invention phosphoric acid already contained is always advantageous, so that in a preferred embodiment the proportion of phosphoric acid in the acidic aqueous medium of the pre-cleaning is at least 60%, particularly preferably at least 80%, based on the total acid in points.
  • the total phosphate content is at least 3 g/kg, particularly preferably at least 5 g/kg, particularly preferably at least 10 g/kg particularly preferably at least 20 g/kg, but preferably less than 50 g/kg, each calculated as PO 4 and based on the acidic aqueous agent of the pre-cleaning.
  • Additivation of the aqueous medium of the preclean with surfactants can be beneficial in aiding the removal of electrocoat residues and is optional within the scope of the present invention.
  • Preferred surface-active substances are organic surfactants, particularly preferably non-ionic organic surfactants.
  • Particularly suitable representatives of non-ionic organic surfactants with high compatibility with alkaline cleaning/degreasing following the pre-cleaning are ethoxylated and/or propoxylated C8-C12, preferably C8-C10, fatty alcohols with a degree of ethoxylation of 5-11 and a degree of propoxylation of 1- 7, which can each be present at least partially end-capped with C1-C4 monoalcohols.
  • the pre-cleaning of the transport pairs consisting of the conveyor frame and the component to be coated in the method according to the invention only involves the separation of residues adhering to the conveyor frames Dip paint residues and thus the prevention of the formation of incrustations on the same, there is usually no need for further additives to the aqueous agent used in the pre-cleaning, e.g. for the purpose of chemical conditioning of the surfaces of the components to be coated.
  • the aqueous composition in the pre-cleaning therefore contains a total of less than 10 g/kg, particularly preferably less than 1 g/kg of organic compounds and further preferably less than 0.1 g/kg, particularly preferably less than 0.01 g/kg of dispersed phosphates calculated as PO 4 .
  • the aqueous agent in the pre-cleaning contains both less than 0.1 g/kg, preferably less than 0.01 g/kg, of dispersed phosphates and less than 10 g/kg, preferably less than 1 g/kg. kg, of other dissolved compounds which, in the case of pre-cleaning in the process according to the invention, do not represent an acid with a pKa value above 2.5 and below 5.5.
  • the pre-cleaning of at least that part of each conveyor frame that has been brought into contact with the cathodic electrocoating, and preferably also of the component that is held by the conveyor frame and is to be coated with an anti-corrosion coating is preferably carried out by means of immersion, impingement and/or spraying, the latter preferably with a spray pressure of at least 2 bar.
  • the temperature of the acidic aqueous agent during the application in the pre-cleaning is preferably in the range from 40 to 60°C.
  • the contact time varies depending on the application and plant, but is preferably between 5 and 60 seconds, particularly preferably between 10 and 30 seconds.
  • the preparation for good wetting of the conveyor frames with the acidic aqueous agent of the pre-cleaning and for better removal of the electrophoretic paint residues is brought into contact with an aqueous wetting agent containing at least one water-soluble alcohol, preferably selected from 1,2 - Propanediol, ethylene glycol, glycerol, 1,4-butanediol and/or at least one water-soluble glycol ether, preferably a mono-alkyl ether having not more than 4 carbon atoms, of di- or tripropylene(ethylene) glycol, wherein at least that part of the conveyor frame which is in the pre-cleaning is brought into contact with the acidic aqueous agent, after the electrocoating, but before the pre-cleaning, preferably also before the conveyor frame to be coated anti-corrosion Component receives, is brought into contact with the aqueous wetting agent.
  • an aqueous wetting agent containing at least one water-soluble alcohol, preferably selected from 1,2 - Prop
  • an alcohol or glycol ether is water-soluble in the context of the present invention if at least 10 g of the alcohol or glycol ether are dissolved in a homogeneous phase to be resolved.
  • the contacting with the aqueous wetting agent preferably takes place for at least 5 seconds, particularly preferably for at least 10 seconds, but preferably not longer than 60 seconds.
  • a passivation in the sense of the present invention characterizes at least one wet-chemical treatment step, during which an essentially inorganic coating is produced on at least one surface of a metallic material of the component to be protected against corrosion in a layer coverage of at least 10 mg/m 2 .
  • a passivation is then essentially inorganic if the area-related ratio of TOC content to layer coverage is less than 0.2 in milligrams per square meter, the TOC content being differential gravimetrically after pyrolysis of a dried passivation in a nitrogen atmosphere at a peak metal temperature of 600 °C is determined.
  • the passivation is based on acidic aqueous treatment solutions containing dissolved phosphates and/or water-soluble compounds of the elements Zr, Ti and/or Si, very particularly preferably phosphating, in particular zinc phosphating, which is usually carried out using acidic aqueous solutions containing 0 3-3 g/kg of zinc ions and 5-50 g/kg of phosphate ions is applied and preferably provides layer weights in the range of 0.5-4 g/m 2 calculated as PO 4 .
  • Zinc phosphating usually includes several wet-chemical treatment stages, since activation of the metal surfaces before the actual zinc phosphating, i.e.
  • the process according to the invention ensures that phosphate ions from the passivation are not carried over into the electrophoretic coating via paint adhesions on the conveyor frames, so that the dip coating is not destabilized by increased phosphate input in the process according to the invention is to be feared.
  • the method according to the invention therefore relates to the anti-corrosion coating of metallic components in series, comprising at least cleaning/degreasing, zinc phosphating and cathodic electrocoating, each as a wet-chemical treatment stage, with the treatment stage of cleaning/degreasing always being that of zinc phosphating in the process sequence for the anti-corrosion coating and is based on an aqueous cleaning solution with a pH above 6, and the treatment stage of the cathodic electrocoating always follows that of the zinc phosphating in the process sequence for the anti-corrosion coating, in which each component to be pretreated in the series of one Conveyor frame was added, then the transport pair consisting of component and conveyor frame through the wet-chemical treatment stages according to the process sequence and the transport pair is only separated from one another after the last treatment stage and a component with an anti-corrosion coating is ejected, and then the conveyor frame released in this way picks up the next component in the series in order to run through the process sequence again for the purpose
  • the treatment step following the pre-cleaning and the passivation follows immediately, ie with or without an intermediate rinsing step, but without a drying step.
  • Immediately in this context means without one or more intervening wet chemical Treatment steps that are not rinsing steps. If, in the context of the present invention, reference is made to carrying out a "rinsing step", this always refers to a process which is solely intended to remove a wet film adhering to the component from an immediately preceding wet-chemical treatment step from the surface of the component and in this way to prevent components from being carried over from wet-chemical treatment steps to subsequent ones.
  • a “drying step” in the sense of the present invention denotes a process in which the surfaces of the metallic component that have a wet film are to be dried with the aid of technical measures, for example supplying thermal energy or transferring an air stream.
  • the process sequence for the anti-corrosion pretreatment of components in series is followed by the baking of the electrophoretic paint to form a hardened coating, with conveyor frames, which are not such conveyor frames, which are used in the process sequence of the anti-corrosion Belong to pre-treatment, pick up the pre-treated components and transfer them to the baking stage and, if necessary, subsequent stages for further coating.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Claims (15)

  1. Procédé destiné au revêtement anticorrosion de pièces métalliques en série, comprenant au moins un nettoyage/dégraissage, une passivation et un laquage par trempage électrophorétique cathodique, respectivement en tant qu'étape de traitement chimique par voie humide, l'étape de traitement de nettoyage/dégraissage précédant toujours celle de passivation dans la séquence de processus pour le revêtement anticorrosion et s'effectuant sur la base d'une solution de nettoyage aqueuse dont le pH est supérieur à 6, et l'étape de traitement de laquage par trempage électrophorétique cathodique suivant toujours celle de passivation dans la séquence de processus pour le revêtement anticorrosion, dans laquelle chaque pièce de la série à prétraiter est reçue par un châssis de convoyeur, puis la paire de transport constituée de la pièce et du châssis de convoyeur étant guidée à travers les étapes de traitement chimique par voie humide selon la séquence de processus et les éléments de la paire de transport n'étant séparés l'un de l'autre qu'après la dernière étape de traitement et une pièce revêtue d'une protection anticorrosion étant évacuée, après quoi le châssis de convoyeur ainsi libéré recevant une pièce suivante de la série afin de réaliser de nouveau la séquence de processus en vue du revêtement anticorrosion de ladite pièce, le châssis de convoyeur réalisant la séquence de processus aussi souvent que nécessaire pour revêtir la série de pièces d'une protection anticorrosion, caractérisé en ce qu'au moins la partie de chaque châssis de convoyeur mise en contact avec le laquage par trempage dans le laquage par trempage électrophorétique cathodique est mise en contact dans un pré-nettoyage, après la dernière étape de traitement et après la réception d'une pièce suivante à prétraiter, mais avant l'étape de traitement de nettoyage/graissage, avec un agent aqueux présentant une teneur totale en acide d'au moins 3 points et contenant de l'acide phosphorique.
  2. Procédé selon la revendication 1, caractérisé en ce que le laquage par trempage électrophorétique cathodique est basé sur un laquage par trempage contenant une résine époxy comme agent liant, laquelle est à son tour est de préférence choisie parmi les polyépoxydes modifiés par des amines, et comprenant en outre de préférence des composés organiques contenant des groupes isocyanate bloqués et/ou non bloqués en tant que durcisseur et, de manière particulièrement préférée, comprenant en outre au moins un composé soluble dans l'eau de l'élément bismuth et/ou de l'élément yttrium.
  3. Procédé selon la revendication 2, caractérisé en ce que le pH du milieu aqueux du pré-nettoyage est inférieur à 5,5, de préférence inférieur à 5,0, de manière particulièrement préférée inférieur à 4,5, mais de préférence ne tombe pas en dessous d'un pH de 2,5.
  4. Procédé selon une ou les deux revendications précédentes 2 et 3, caractérisé en ce que la teneur totale en acide de l'agent aqueux du pré-nettoyage est d'au moins 5 points, de préférence d'au moins 10 points, de manière particulièrement préférée d'au moins 20 points.
  5. Procédé selon une ou plusieurs des revendications précédentes 2 à 4, caractérisé en ce que l'agent aqueux du pré-nettoyage présente une teneur totale en phosphate d'au moins 3 g/kg, de préférence d'au moins 5 g/kg, de manière particulièrement préférée d'au moins 10 g/kg, de manière tout particulièrement préférée d'au moins 20 g/kg, mais de préférence inférieure à 50 g/kg, respectivement calculée en tant que PO4 et par rapport à l'agent aqueux.
  6. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que l'agent aqueux du pré-nettoyage contient en outre des substances tensioactives, de préférence des tensioactifs, de manière particulièrement préférée des tensioactifs non ioniques, qui sont eux-mêmes choisis de préférence parmi les alcools gras en C8-C12 éthoxylés et/ou propoxylés avec un degré d'éthoxylation de 5 à 11 et un degré de propoxylation de 1 à 7.
  7. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce qu'au moins la partie de chaque châssis de convoyeur qui a été mise en contact avec le laquage par trempage électrophorétique cathodique, et de préférence également la pièce qui est reçue par le châssis de convoyeur et doit être revêtue avec une protection anticorrosion, est mise en contact avec l'agent aqueux à l'étape de traitement de pré-nettoyage par immersion, projection et/ou pulvérisation, cette dernière comportant de préférence une pression de pulvérisation d'au moins 2 bars.
  8. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la mise en contact avec l'agent aqueux lors du pré-nettoyage s'effectue à une température située dans la plage de 40 à 60 °C.
  9. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la partie du châssis de convoyeur qui est mise en contact avec l'agent aqueux lors du pré-nettoyage est mise en contact, après le laquage par trempage électrophorétique cathodique, mais avant le pré-nettoyage, et également de préférence avant que le châssis de convoyeur reçoive la pièce à revêtir d'une protection anticorrosion, avec un agent mouillant aqueux contenant au moins un alcool soluble dans l'eau, de préférence choisi parmi le 1,2-propanediol, l'éthylène glycol, le glycérol, le 1,4-butanediol et/ou au moins un éther de glycol soluble dans l'eau, de préférence un éther de mono-alkyle comportant au plus 4 atomes de carbone de dipropylène(éthylène)glycol ou de tripropylène(éthylène)glycol.
  10. Procédé selon la revendication 9, caractérisé en ce que la mise en contact avec l'agent mouillant s'effectue pendant au moins 5 secondes, de préférence pendant au moins 10 secondes, mais de préférence pas plus de 60 secondes.
  11. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que l'étape de traitement suivant respectivement le pré-nettoyage et la passivation les suit sans étape de séchage et sans une ou plusieurs étapes de traitement chimique par voie humide intermédiaires qui ne représentent pas des étapes de rinçage.
  12. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que l'étape de traitement de nettoyage/dégraissage suit immédiaitement celle de pré-nettoyage sans étape de rinçage intermédiaire et sans étape de séchage.
  13. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la passivation s'effectue sur la base d'une solution de traitement aqueuse acide contenant des phosphates dissous, de préférence d'une phosphatation, de manière particulièrement préférée d'une phosphatation au zinc.
  14. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que l'étape de traitement de nettoyage/dégraissage s'effectue sur la base d'une solution de nettoyage aqueuse alcaline dont le pH est de préférence supérieur à 8, de manière particulièrement préférée supérieur à 10.
  15. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la séquence de processus destinée au revêtement anticorrosion de pièces en série est suivie par la cuisson de la laque par trempage électrophorétique cathodique pour former un laquage durci, de préférence à nouveau des châssis de convoyeur, lesquels ne sont pas les châssis de convoyeur appartenant à la séquence de processus du revêtement anticorrosion, recevant les pièces revêtues et les transférant vers l'étape de cuisson et, éventuellement, vers des étapes ultérieures en vue d'un autre revêtement.
EP19720648.5A 2018-05-16 2019-05-02 Nettoyage des râteliers dans un procédé de dépôt électrophoréctique Active EP3794167B1 (fr)

Applications Claiming Priority (2)

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EP18172576.3A EP3569743A1 (fr) 2018-05-16 2018-05-16 Nettoyage de charriot dans un cycle d'opération de laquage par électro-immersion
PCT/EP2019/061235 WO2019219395A1 (fr) 2018-05-16 2019-05-02 Nettoyage de châssis de transport dans une succession de processus de peinture électrophorétique par immersion

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EP3794167B1 true EP3794167B1 (fr) 2022-11-02

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EP19720648.5A Active EP3794167B1 (fr) 2018-05-16 2019-05-02 Nettoyage des râteliers dans un procédé de dépôt électrophoréctique

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US5084263A (en) * 1989-07-24 1992-01-28 Mccoy/Defalco Electrochemics, Inc. Method of preparing inorganic polymeric water complexes and products so produced
US8877029B2 (en) * 2007-08-15 2014-11-04 Ppg Industries Ohio, Inc. Electrodeposition coatings including a lanthanide series element for use over aluminum substrates
DE102007057185A1 (de) 2007-11-26 2009-05-28 Henkel Ag & Co. Kgaa Zirconiumphosphatierung von metallischen Bauteilen, insbesondere Eisen
PL2503025T3 (pl) 2011-03-22 2013-12-31 Henkel Ag & Co Kgaa Chroniąca przed korozją, wielostopniowa obróbka metalowych elementów konstrukcyjnych o powierzchniach cynkowych
DE102011051879B4 (de) * 2011-07-15 2023-11-09 Dürr Systems Ag Anlage und Verfahren zur Oberflächenbehandlung von Werkstücken sowie Verwendung einer solchen Anlage zum Lackieren von Werkstücken
DE102014225237B3 (de) * 2014-12-09 2016-04-28 Henkel Ag & Co. Kgaa Verfahren zur nasschemischen Vorbehandlung einer Vielzahl von Eisen- und Aluminiumbauteilen in Serie
US20160258079A1 (en) * 2015-03-04 2016-09-08 TKS Industrial Company Method and apparatus for removing residue from electrocoated articles
DE102015209909A1 (de) * 2015-05-29 2016-12-01 Henkel Ag & Co. Kgaa Konditionierung vor einer Konversionsbehandlung von Metalloberflächen
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DE102016206418A1 (de) * 2016-04-15 2017-10-19 Henkel Ag & Co. Kgaa Unterdrückung anlagenbedingter phosphatüberschleppung in einer prozessfolge zur tauchlackierung

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CN112119184A (zh) 2020-12-22
WO2019219395A1 (fr) 2019-11-21
US20210062356A1 (en) 2021-03-04
EP3794167A1 (fr) 2021-03-24

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