EP3336219B1 - Procédé de prétraitement de protection anticorrosion et de nettoyage de composants métalliques - Google Patents

Procédé de prétraitement de protection anticorrosion et de nettoyage de composants métalliques Download PDF

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Publication number
EP3336219B1
EP3336219B1 EP16205069.4A EP16205069A EP3336219B1 EP 3336219 B1 EP3336219 B1 EP 3336219B1 EP 16205069 A EP16205069 A EP 16205069A EP 3336219 B1 EP3336219 B1 EP 3336219B1
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EP
European Patent Office
Prior art keywords
component
acidic aqueous
aqueous composition
carbon atoms
particularly preferably
Prior art date
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EP16205069.4A
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German (de)
English (en)
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EP3336219A1 (fr
Inventor
Jerzy-Tadeusz Wawrzyniak
Nils BONGARTZ
Dalija Vrban
Henry A. Rossmaier
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL16205069T priority Critical patent/PL3336219T3/pl
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP16205069.4A priority patent/EP3336219B1/fr
Priority to ES16205069T priority patent/ES2734254T3/es
Priority to PCT/EP2017/079534 priority patent/WO2018114157A1/fr
Priority to KR1020197020392A priority patent/KR102489194B1/ko
Priority to CN201780077935.1A priority patent/CN110073032B/zh
Priority to JP2019533030A priority patent/JP7145157B2/ja
Priority to CA3047184A priority patent/CA3047184A1/fr
Publication of EP3336219A1 publication Critical patent/EP3336219A1/fr
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Publication of EP3336219B1 publication Critical patent/EP3336219B1/fr
Priority to US16/432,125 priority patent/US11761092B2/en
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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
    • C23C22/05—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
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/08—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/268—Carbohydrates or derivatives thereof
    • 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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also 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
    • C23C22/05—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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50—Treatment of iron or alloys based thereon
    • 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
    • C23C22/76—Applying the liquid by spraying
    • 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
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • 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
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—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
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • 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
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/12—Light metals
    • C23G1/125—Light metals aluminium
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—Metals

Definitions

  • the present invention relates to a method for corrosion-protecting and cleaning pretreatment of metallic components which are at least partially made of metallic materials of the elements iron, zinc and / or aluminum, using an acidic aqueous composition containing in addition to the conversion of the metal surface causing water-soluble compounds of the elements Zr and / or Ti is a mixture of an aliphatic diol and an aliphatic saturated polyhydroxy compound. Also included is a chromium (VI) -free aqueous composition based on the aforementioned ingredients which provides excellent cleaning and simultaneous corrosion protection conversion of engineering metal surfaces in one process step.
  • VI chromium
  • a conversion coating is often applied prior to the application of a protective and / or decorative coating, such as a paint, on metal substrates, in particular metallic components containing the materials iron, zinc and / or aluminum.
  • a protective and / or decorative coating such as a paint
  • the industrial coating of a variety of components requires a pre-treatment in series, in which each component undergoes different treatment stages in a predetermined order.
  • Such pretreatment in series usually comprises the separate process steps of the purification and the pretreatment and, where appropriate, the coating, wherein each process step is followed regularly by a rinsing step for the removal of active components from the preceding process step.
  • the step of wet-chemical cleaning of the components is often tailored depending on the substrate and the type of contamination, with a variety of caustic alkaline or acid cleaner and neutral detergent is available to rid the components of conventional contaminants such as corrosion protection oils, cutting oils and coolants and to condition their metallic surfaces for subsequent wet chemical pretreatment. Meanwhile conversions often carried out on an industrial scale aiming at temporary corrosion protection and the provision of a suitable paint adhesion base, the metal surfaces provide amorphous inorganic coatings based on the elements Zr and / or Ti.
  • Such conversion treatments which for the stated purpose are wet-chemically 100 mg / m 2 based on the aforementioned elements, have the advantage over conventional partially crystalline conversion layers based on phosphates to consume less active components and thus resource-saving and more efficient due to a lower number of process stages and be formulated phosphate-free can.
  • the prior art also describes such conversion treatment methods in which both the component is cleaned and the metal surfaces of the component are converted in one step.
  • the WO 2012/178003 A2 describes an acidic aqueous composition suitable for the purification and conversion of metal surfaces containing a source of zirconium dissolved in water and a mixture of a cationic and nonionic surfactant, preferably alkyl polyglycol ethers, ethoxylated fatty amines and fatty alcohols and EO / PO block copolymers and cationic surfactants as nonionic surfactant quaternized alkylammonium salts are used.
  • a cationic and nonionic surfactant preferably alkyl polyglycol ethers, ethoxylated fatty amines and fatty alcohols and EO / PO block copolymers and cationic surfactants as nonionic surfactant quaternized alkylammonium salts are used.
  • the EP 2 159 045 A1 discloses lacquer-coated aluminum sheet which, by surface treatment with a chromium-free treatment solution, obtains compounds of the element zirconium and polyitaconic acid as well as sugar alcohols for the complexation of aluminum ions and subsequent lacquering.
  • US 4,148,670 describes acidic aqueous treatment solutions for aluminum to improve the adhesion of a subsequent coating containing compounds of zirconium and / or titanium, dissolved fluoride and phosphate and optionally polyhydroxy compounds having not more than 6 carbon atoms.
  • the object was to develop an alternative conversion treatment stage, in which the cleaning of a metallic component can be performed in one step simultaneously with the conversion, the method should be particularly suitable for components containing the material iron.
  • the cleaning and conversion at the lowest possible temperatures ideally well below 40 ° C, should be possible in order to avoid the formation of rust on the surfaces of the material iron and to significantly reduce overall energy consumption in the process.
  • the components treated according to the present invention can be any arbitrarily shaped and configured spatial structures originating from a fabrication process, in particular also semi-finished products such as strips, sheets, rods, tubes, etc., and composite structures joined together from the aforementioned semifinished products, wherein the semifinished products preferably by gluing, welding and / or flanging to the composite structure are connected together.
  • a metallic material consists predominantly of the elements iron, zinc and / or aluminum if the atomic proportion of these elements in the material as a whole is greater than 50 at.%.
  • the metallic material can also be a metallically coated substrate insofar as the metallic coating has a layer thickness of at least 1 ⁇ m and consists of more than 50 at.% Of the constituent elements defined above.
  • Such materials are all plated iron materials such as electrolytically or hot dip galvanized steel, preferably platings in the form of zinc (Z), aluminum-silicon (AS), zinc-magnesium (ZM), zinc-aluminum (ZA), aluminum-zinc (AZ). or zinc-iron (ZF).
  • the metal surfaces are freed in one step both from impurities from upstream production stages such as corrosion protection oils, cutting oils and coolants and applied to a corrosion protective Lackhaftground in the form of a conversion coating.
  • impurities from upstream production stages such as corrosion protection oils, cutting oils and coolants
  • a corrosion protective Lackhaftground in the form of a conversion coating.
  • sufficient cleaning and corrosion-protective conversion of the metal surfaces can be achieved in the process according to the invention even at comparatively low working temperatures.
  • the inventive method allows the pretreatment of components in systems in which only a few treatment stages are provided, which additionally contributes to the process economy, that the method can be operated even at low operating temperatures.
  • the treatment of such components has proven to be advantageous, which consist at least partially of ferrous materials.
  • ferrous materials On the surfaces of the iron materials can be found in comparison to the other metallic materials, a further improvement in the cleaning effect and the mediation of a corrosion-protective paint adhesion base.
  • An iron material is characterized in that its content of iron is more than 50 at.%.
  • Preferred iron materials are steel, wherein steel includes metallic materials whose mass fraction of iron is greater than that of each other element, and their carbon content is less than 2.06 wt .-% without regard to carbides.
  • a significant advantage of the method according to the invention is that a cleaning of the metallic surfaces of the component of aids based on organic compounds such as corrosion protection oils, cutting oils and cooling lubricants from upstream production stages succeed even at relatively low operating temperatures.
  • the contacting of the acidic aqueous composition therefore takes place at a temperature of the composition of less than 40.degree. C., more preferably of less than 35.degree. C., more preferably of less than 30.degree preferably at least 20 ° C.
  • the contacting of the acidic aqueous composition in the process according to the invention by spraying or spraying, particularly preferably by spraying, particularly preferably at an injection pressure of at least 1 bar, for optimum cleaning and rapid conversion of To achieve metal surfaces.
  • auxiliary agents based on organic compounds occurring when the component is brought into contact with the acidic aqueous composition, it is entirely possible to dispense with a preceding purification step.
  • the method according to the invention therefore takes place immediately before contacting the component with the acidic aqueous composition, preferably by spraying or spraying, no wet chemical cleaning of the component.
  • a wet-chemical cleaning according to the invention is a cleaning by contacting with a water-based composition containing a total of at least 0.1 wt .-% of surfactants and / or wetting agents, wherein surfactants and / or wetting agents include all organic compounds, the Surface tension of water at 20 ° C and a proportion of 0.1 wt .-% determined by the Wilhelmy plate method lower.
  • the process according to the invention is preferably followed by at least partial coating of the regions of the component previously in contact with the acidic aqueous composition were brought, preferably a dip coating, in particular an electrocoating, or powder coating.
  • a "rinsing step" in the sense of the present invention denotes a process which is intended solely to remove as far as possible active components from an immediately preceding wet-chemical treatment step, which are dissolved in a wet film adhering to the component, by means of a rinsing solution from the surface of the component. without replacing the active components to be removed by others.
  • Active components in this context are constituents contained in a liquid phase which cause an analytically detectable coating of the metal surfaces of the component with elemental constituents of the active components.
  • a “drying step” in the context of the present invention refers to a process in which the surfaces of the metallic component having a wet film are to be dried with the aid of technical measures, for example supplying thermal energy or passing an air stream.
  • the aliphatic diol of component a) to be used in a process according to the invention is preferably selected from diols whose hydroxyl groups are not connected to each other by more than 3 carbon atoms, and is more preferably selected from acyclic alkanediols containing not more than 8 carbon atoms but preferably at least 5 carbon atoms and more preferably 2-methylpentane-2,4-diol.
  • the aliphatic polyhydroxy compound according to component b) to be used in a process according to the invention is an aliphatic compound having more than two hydroxyl groups, preferably more than three hydroxyl groups, wherein preferably at least two hydroxyl groups are bonded together by not more than two carbon atoms ("vicinal hydroxyl groups").
  • the polyhydroxy compounds according to component b) are particularly preferably an alditol, which in turn preferably has not more than 6 carbon atoms and is particularly preferably selected from erythritol, threitol, xylitol, arabitol, ribitol, mannitol or sorbitol, and particularly preferably sorbitol.
  • Excellent cleaning performance is achieved when the mass-related ratio of polyhydroxy compounds according to component b) to diols according to component a) is at least 0.4. Such a relative minimum amount of polyhydroxy compounds according to component b) is therefore preferred in the process according to the invention. Particularly preferably, the aforementioned ratio is at least 1.0, particularly preferably at least 2.0. At too high relative amounts of polyhydroxy compounds according to component b) can be maintained with otherwise constant total amount of active components a) and b) the good cleaning performance and the simultaneous conversion of the metal surface loses its homogeneity.
  • the mass-related ratio of polyhydroxy compounds according to component b) to diols according to component a) is not greater than 20.0, particularly preferably not greater than 10.0, very particularly preferably not greater than 6.0 is.
  • the proportion of water-soluble compounds of the elements Zr and / or Ti according to component c) in an acidic aqueous composition of the inventive method total of at least 0.002 wt .-%, particularly preferably at least 0.005 wt .-%, calculated as the amount of Zr, wherein for economic reasons and to avoid the over-pickling of the conversion layer preferably not more than 0.2 wt .-% of water-soluble compounds of the elements Zr and / or Ti calculated as amount of Zr in an acidic aqueous composition of the method according to the invention are included.
  • Suitable representatives of the water-soluble compounds of the elements Zr and / or Ti according to component c) are compounds which dissociate in aqueous solution into anions of fluorocomplexes.
  • 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 compounds.
  • fluorine-free compounds of the elements Zr or Ti, in particular the element Zr can be used according to the invention as water-soluble compounds, for example (NH 4 ) 2 Zr (OH) 2 (CO 3 ) 2 or TiO (SO 4 ).
  • fluorometalates of the elements Zr and / or Ti and their fluoro acids are present in the acidic aqueous composition.
  • an acidic composition of the process according to the invention contains, as component d), a source of fluoride ions which is required for a homogeneous and reproducible corrosion-protecting conversion coating on the metal surfaces of the component.
  • the source of fluoride ions is any inorganic compound that is capable of being dissolved or dispersed in water to liberate fluoride ions.
  • a preferred source of fluoride ions are complex or simple fluorides. Simple fluorides are understood to mean hydrofluoric acid and its salts, such as alkali fluorides, ammonium fluoride or ammonium bifluoride, whereas complex fluorides are coordination compounds according to the invention in which fluorides are coordinated as ligands of one or more central atoms. Accordingly, preferred representatives of the complex fluorides are the aforementioned fluorine-containing complex compounds of the elements Zr, Ti or Si.
  • the proportion of compounds which are a source of fluoride ions in an acidic aqueous composition of the process according to the invention is preferably at least such that an amount of free fluoride of at least 0.01 g / kg, but preferably not more than 0 , 6 g / kg, particularly preferably not more than 0.2 g / kg in the acidic aqueous composition.
  • the free fluoride content is determined by means of calibrated fluoride-sensitive electrode directly in the acidic aqueous composition at 20 ° C.
  • the molar ratio of total fluoride content to the total amount of elements Zr and / or Ti according to component c) is greater is 4.5, preferably greater than 5.0, more preferably greater than 5.5.
  • the total fluoride content is determined with a fluoride-sensitive electrode in a TISAB-buffered aliquot of an acidic aqueous composition of the method according to the invention at 20 ° C (TISAB: "Total Lonic Strength Adjustment Buffer”), wherein the volume-related mixing ratio of buffer to aliquot the acidic aqueous composition is 1: 1.
  • the TISAB buffer is prepared by dissolving 58 g of NaCl, 1 g of sodium citrate and 50 ml of glacial acetic acid in 500 ml of deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ) and adjusting the pH to 5.3 by 5N NaOH and making up to a total volume of 1000 ml again with deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ).
  • the inventive cleaning and simultaneous conversion of the metal surfaces of the component to a corrosion-protective coating based on the elements Zr and / or Ti takes place in an acidic aqueous composition.
  • the pH of the acidic aqueous composition is preferably above 2.0, more preferably above 3.0, especially preferably above 4.0, since even low pickling rates are sufficient to achieve good cleaning of the metal surfaces bring about.
  • a certain pickling rate is required for the formation of an alkaline diffusion layer on the metal surfaces, within which the precipitation of the coating constituents takes place.
  • the acidic aqueous composition has a pH below 6.0, more preferably below 5.5, wherein the acidic aqueous composition preferably has a free acid content of at least 1 point.
  • the free acid is determined by diluting 2 ml of the acidic aqueous composition to 50 ml with deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ), titrating with 0.1 N sodium hydroxide solution to a pH of 5.5. The consumption of acid solution in ml indicates the score of the free acid.
  • an acidic aqueous composition additionally contains calcium and / or magnesium ions in the process according to the invention, particularly preferably a total of at least 0.01% by weight of calcium and magnesium ions, especially preferably at least 0.01% by weight of magnesium ions.
  • Preferred sources of magnesium and / or calcium ions are their nitrates.
  • the acidic aqueous composition for accelerating the conversion of the metal surfaces which are brought into contact with the acidic composition additionally contains at least one water-soluble compound which is a source of copper ions, preferably in the form of a water-soluble salt
  • copper ions preferably in the form of a water-soluble salt
  • the presence of copper ions is also beneficial for the anti-corrosive properties of the conversion coating resulting from the conversion to the metallic surfaces of the components.
  • the content of copper ions from water-soluble compounds in the acidic aqueous composition for this purpose is preferably at least 0.001 g / kg, more preferably at least 0.005 g / kg.
  • the content of copper ions is preferably not more than 0.1 g / kg, more preferably not more than 0.05 g / kg, otherwise the deposition of elemental copper begins to dominate over the conversion layer formation.
  • the acidic aqueous composition additionally contains at least one water-soluble compound which has a standard reduction potential at pH 0 above +0.6 V (SHE) and is preferably selected from inorganic nitrogen compounds, more preferably from nitric acid and / or nitrous acid and their salts.
  • SHE standard reduction potential at pH 0 above +0.6 V
  • the proportion of water-soluble compounds for accelerating the conversion layer formation is preferably at least 0.001 mol / L, preferably at least 0.01 mol / L, but for reasons of economy, preferably less than 0.2 mol / L.
  • the weight fraction of organic compounds having a boiling point or decomposition point above 150 ° C. in the acidic aqueous composition which are not compounds of components a) and b) is less than 50%, based on the total content of organic compounds. , more preferably less than 20%, most preferably less than 10%.
  • a composition is "phosphate-free" if the proportion of phosphates dissolved in water is less than 100 mg / kg, preferably less than 20 mg / kg calculated as the amount of phosphorus.
  • a composition is "chromium (VI) -free” if the proportion of compounds of the element chromium dissolved in water in the oxidation state + VI is less than 100 mg / kg, preferably less than 20 ppm.
  • Preferred embodiments of the acidic aqueous chromium (VI) - and phosphate-free composition are analogous to those previously described in the context of the inventive method for the cleaning and corrosion-protective pretreatment of a metallic component with respect to the acidic aqueous composition.
  • Oiled steel sheets (Gardobond® MBS 30, Chemetall GmbH) were subjected to a cleansing conversion treatment.
  • the treatment was carried out in a spray chamber at an injection pressure of 1-2 bar for 60 seconds at 25 ° C and a pH of the aqueous conversion solution of 4.6.
  • the conversion solution contained 0.16 g / L hexafluorozirconic 0.32 g / L Magnesium nitrate hexahydrate 0.3 g / L sorbitol 0.1 g / L 2-methylpentane-2,4-diol

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Molecular Biology (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Detergent Compositions (AREA)

Claims (15)

  1. Procédé de prétraitement de nettoyage et de protection anticorrosion d'un composant métallique qui est composé au moins partiellement d'un matériau constitué majoritairement d'un ou de plusieurs des métaux suivants : fer, zinc et/ou aluminium, par mise en contact du composant avec une composition aqueuse acide contenant
    a) au moins 0,003 % en poids de diols aliphatiques présentant au moins 4 atomes de carbone, mais pas plus de 10 atomes de carbone ;
    b) au moins 0,01 % en poids de composés polyhydroxy saturés aliphatiques, qui présentent plus de deux groupes hydroxyle et au moins 4, mais pas plus de 8 atomes de carbone ;
    c) au moins un composé hydrosoluble des éléments Zr et/ou Ti ;
    d) au moins une source hydrosoluble pour des ions fluorure.
  2. Procédé selon la revendication 1, caractérisé en ce que le rapport exprimé en masse entre les composés polyhydroxy selon le composant b) et les diols selon le composant a) est d'au moins 0,4, de préférence d'au moins 1,0, de manière particulièrement préférée d'au moins 2,0, mais de préférence pas supérieur à 20,0, de manière particulièrement préférée pas supérieur à 10,0, de manière tout particulièrement préférée pas supérieur à 6,0.
  3. Procédé selon l'une ou les deux des revendications précédentes, caractérisé en ce que le diol aliphatique selon le composant a) est choisi parmi des diols dont les groupes hydroxyles sont reliés entre eux par pas plus de 3 atomes de carbone.
  4. Procédé selon la revendication 3, caractérisé en ce que le diol aliphatique selon le composant a) est choisi parmi des alcanediols acycliques qui ne présentent pas plus de 8 atomes de carbone, mais présentent toutefois au moins 5 atomes de carbone, et est en particulier du 2-méthylpentane-2,4-diol.
  5. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que les composés polyhydroxy selon le composant b) présentent plus de trois groupes hydroxyles, au moins deux groupes hydroxyles étant de préférence reliés entre eux par pas plus de deux atomes de carbone, et étant de manière particulièrement préférée un alditol, qui présente en revanche de préférence pas plus de 6 atomes de carbone et est choisi de manière particulièrement préférée parmi l'érythritol, le thréitol, le xylitol, l'arabitol, le ribitol, le mannitol ou le sorbitol, et est de manière particulièrement préférée le sorbitol.
  6. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que l'on trouve au total au moins 0,002 % en poids, de préférence au moins 0,005 % en poids de composés hydrosolubles des éléments Zr et/ou Ti, calculé en tant que quantité de Zr dans la composition aqueuse acide, mais toutefois de préférence au total pas plus de 0,2 % en poids de composés hydrosolubles des éléments Zr et/ou Ti, calculé en tant que quantité de Zr.
  7. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que la composition aqueuse acide présente une valeur pH inférieure à 6,0, de préférence inférieure à 5,5, de préférence toutefois supérieure à 2,0, de manière particulièrement préférée supérieure à 3,0, en particulier de manière préférée supérieure à 4,0, la composition aqueuse acide présentant de préférence une teneur en acide libre d'au moins 1 point.
  8. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que la composition aqueuse acide contient la source hydrosoluble pour les ions fluorure dans une quantité telle que la part en fluorure libre vaut au moins 10 mg/kg.
  9. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que la composition aqueuse acide contient en outre des ions calcium et/ou magnésium, de préférence au total au moins 0,01 % en poids d'ions calcium et magnésium, de manière particulièrement préférée au moins 0,01 % en ions magnésium.
  10. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que le composant est constitué au moins partiellement d'un matériau en fer.
  11. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que la mise en contact s'effectue par application ou pulvérisation, de préférence par pulvérisation, de manière particulièrement préférée à une pression de pulvérisation d'au moins 1 bar.
  12. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que la composition aqueuse acide présente, lors de la mise en contact, une température inférieure à 40 °C, de préférence inférieure à 35 °C, de manière particulièrement préférée inférieure à 30 °C, mais de préférence d'au moins 20 °C.
  13. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que, immédiatement après la mise en contact du composant avec la composition aqueuse acide-avec ou sans étape de rinçage ou de séchage intermédiaire-il se produit une opération de peinture au moins partielle des zones du composant qui ont été auparavant mises en contact avec la composition aqueuse acide, de préférence une peinture par immersion ou une peinture par poudre.
  14. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que, immédiatement avant la mise en contact du composant avec la composition aqueuse acide dans la seringue, aucun nettoyage chimique liquide du composant n'est effectué.
  15. Composition acide liquide sans chrome(VI) et sans phosphate contenant
    a) de 0,003 à 2 % en poids de diols aliphatiques qui présentent au moins 4 atomes de carbone, mais pas plus de 10 atomes de carbone ;
    b) de 0,01 à 5 % en poids de composés polyhydroxy saturés aliphatiques, qui présentent plus de deux groupes hydroxyle et au moins 4, mais pas plus de 8 atomes de carbone ;
    c) de 0,002 à 0,2 % en poids de composés hydrosolubles de l'élément Zr, calculé en tant que quantité en Zr ;
    d) au moins 10 mg/kg en ions fluorure libres.
EP16205069.4A 2016-12-19 2016-12-19 Procédé de prétraitement de protection anticorrosion et de nettoyage de composants métalliques Active EP3336219B1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP16205069.4A EP3336219B1 (fr) 2016-12-19 2016-12-19 Procédé de prétraitement de protection anticorrosion et de nettoyage de composants métalliques
ES16205069T ES2734254T3 (es) 2016-12-19 2016-12-19 Procedimiento para el tratamiento previo de protección contra la corrosión y de limpiado de componentes metálicos
PL16205069T PL3336219T3 (pl) 2016-12-19 2016-12-19 Sposób chroniącej przed korozją i czyszczącej obróbki wstępnej metalicznych elementów konstrukcyjnych
KR1020197020392A KR102489194B1 (ko) 2016-12-19 2017-11-17 금속 부품의 세척 및 항-부식 전환 전처리 방법
PCT/EP2017/079534 WO2018114157A1 (fr) 2016-12-19 2017-11-17 Procédé de prétraitement de protection anti-corrosion et de nettoyage d'éléments métalliques
CN201780077935.1A CN110073032B (zh) 2016-12-19 2017-11-17 金属组件的防腐和清洁预处理的方法
JP2019533030A JP7145157B2 (ja) 2016-12-19 2017-11-17 金属部材の防食および洗浄前処理方法
CA3047184A CA3047184A1 (fr) 2016-12-19 2017-11-17 Procede de pretraitement de protection anti-corrosion et de nettoyage d'elements metalliques
US16/432,125 US11761092B2 (en) 2016-12-19 2019-06-05 Method for corrosion-protective and cleaning pretreatment of metallic components

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EP16205069.4A EP3336219B1 (fr) 2016-12-19 2016-12-19 Procédé de prétraitement de protection anticorrosion et de nettoyage de composants métalliques

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JP (1) JP7145157B2 (fr)
KR (1) KR102489194B1 (fr)
CN (1) CN110073032B (fr)
CA (1) CA3047184A1 (fr)
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CN110073032B (zh) 2021-09-07
EP3336219A1 (fr) 2018-06-20
ES2734254T3 (es) 2019-12-05
KR20190096382A (ko) 2019-08-19
PL3336219T3 (pl) 2019-10-31
JP7145157B2 (ja) 2022-09-30
JP2020502367A (ja) 2020-01-23
KR102489194B1 (ko) 2023-01-16
US20190284700A1 (en) 2019-09-19
CN110073032A (zh) 2019-07-30
CA3047184A1 (fr) 2018-06-28
WO2018114157A1 (fr) 2018-06-28
US11761092B2 (en) 2023-09-19

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