EP4689227A2 - Composition de nettoyage et procédé de nettoyage de surfaces métalliques pour empêcher la corrosion d'un bain de rinçage - Google Patents

Composition de nettoyage et procédé de nettoyage de surfaces métalliques pour empêcher la corrosion d'un bain de rinçage

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Publication number
EP4689227A2
EP4689227A2 EP24718092.0A EP24718092A EP4689227A2 EP 4689227 A2 EP4689227 A2 EP 4689227A2 EP 24718092 A EP24718092 A EP 24718092A EP 4689227 A2 EP4689227 A2 EP 4689227A2
Authority
EP
European Patent Office
Prior art keywords
composition
optionally
constituent
aac
present
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24718092.0A
Other languages
German (de)
English (en)
Inventor
Lara-Marie WASCHKOWSKI
Christoph Kasper
Thorsten LUECKERATH
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemetall GmbH
Original Assignee
Chemetall GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemetall GmbH filed Critical Chemetall GmbH
Publication of EP4689227A2 publication Critical patent/EP4689227A2/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • 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
    • C23C22/73—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
    • 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
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/20—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
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the present invention relates to a method for cleaning of metallic surfaces of substrates, a cleaning composition suitable for use in this method, a concentrate, from which the cleaning composition is obtainable, a method for chemically pretreating cleaned metallic surfaces, a method for coating cleaned and chemically pretreated metallic surfaces, and to substrates having cleaned and/or chemically pretreated and/or coated metallic surfaces obtainable by these methods.
  • metal parts such as manufactured car bodies or parts thereof are usually cleaned with cleaning compositions in order to remove impurities on their surfaces, which may be attached physically or chemically on the metallic surface of the substrate such as residual oils/lubricants/particles/oxidation products etc., before they enter subsequent steps of a following coating process (i.e., applying a conversion coating, an electrodeposition coating and further coatings), since such impurities typically lead to defects in subsequently formed chemical pretreatment layers and further coating layers.
  • cleaning compositions in order to remove impurities on their surfaces, which may be attached physically or chemically on the metallic surface of the substrate such as residual oils/lubricants/particles/oxidation products etc.
  • the cleaning can be conducted in acidic or alkaline medium.
  • alkaline cleaners that contain an alkalinity source such as a hydroxide source, e.g., potassium and/or sodium hydroxide, or another alkalinity source such as (ortho)phosphates and/or carbonates, and varying complexing agents such as phosphonic acids, (condensed) phosphates or borates, since they generally have better cleaning performance than their acidic counterparts.
  • Such cleaners are typically operated in a comparably high pH range of >9.5 such as at pH 9.5 to 10.5, in particular in the automotive industry.
  • the exact pH conditions vary and are dependent on the employed metal substrate to be treated.
  • the pH range selected usually provides an optimal compromise between a sufficient cleaning performance to achieve a desirably entire removal of residual oils, lubricants, particles, oxidation products etc. and an only mild treatment of the substrates such as car bodies or parts thereof to be cleaned, which are often composed of multi-metals, to achieve only low etching rates on these used metal substrates.
  • cleaners are typically operated at even higher pH values such as at pH values of >10.5, e.g., at pH values of > 11 , since iron being present in the steel substrates is not etched at such high pH values, in contrast to other metals such as, e.g., zinc and aluminum.
  • rinse bath corrosion refers to all kinds of corrosion defects such as flash rusting on steel, e.g., on CRS or on HRS (hot rolled steel) or the formation of so-called white spots or pinholes on zinc-coated or zinc-containing substrates, e.g., HDG (hot- dip galvanized steel) or EG (electrolytically galvanized steel), that can be observed in production lines directly after the cleaning stages or in between the rinsing stages. Parameters that contribute to such unwanted rinse bath corrosion defects are, e.g., temperature, transfer times between baths or certain chemical conditions.
  • Flash rust is a common phenomenon observed on iron, which tends to spontaneously start corroding within minutes after cleaning when being contacted with moisture and/or oxygen, resulting in yellow/brownish iron hydroxide/oxide corrosion products on the steel surface.
  • White spots on zinc-coated substrates are local defects that are typically caused by locally too high etching rates, resulting in white corrosion spots that appear as craters under the microscope, in whose interior the zinc layer is almost completely dissolved.
  • Rinse bath corrosion defects are to be entirely avoided in industrial production lines, as they can cause insufficient paint adhesion and/or optical defects after chemical pretreatment and one or more further subsequent coating steps carried out. Removal of such optical defects once present requires additional grinding steps, which have to be carried out later on.
  • rinse bath corrosion defects can potentially represent the starting point for more widespread corrosion and worsen corrosion test results. While the mentioned issues/problems caused by rinse bath corrosion can be found irrespective of the employed chemical pretreatment (e.g., phosphating pretreatment and conversion film formation by use of suitable chemical pretreatment compositions), chemical pretreatment based on making use of compositions comprising zirconium cations, fluorides and organosilanes is particularly vulnerable to said defects and thus, rinse bath corrosion needs to be avoided in particular when and despite making use of such chemical pretreatment compositions.
  • chemical pretreatment e.g., phosphating pretreatment and conversion film formation by use of suitable chemical pretreatment compositions
  • chemical pretreatment based on making use of compositions comprising zirconium cations, fluorides and organosilanes is particularly vulnerable to said defects and thus, rinse bath corrosion needs to be avoided in particular when and despite making use of such chemical pretreatment compositions.
  • Some methods to prevent the formation of rinse bath corrosion are known in the prior art. It is, e.g., possible to add an inhibiting species to the cleaner composition used, which then deposits on the metal surfaces during the cleaning step, and which ideally cannot be washed away in the subsequent rinsing stages, thus protecting the metal surfaces from said corrosion defects.
  • inhibiting species are molybdates, borates and different Si-based compounds such as silicates or reactive (hydrolyzed/pre-condensed) silanes, as well as iron ions.
  • silanes in inter alia cleaning compositions for prevention of pinholes is, e.g., known from US 2015/361382 A1.
  • molybdates in such cleaning compositions with very low phosphate content is, e.g., known from US 2018/057773 A1.
  • molybdates and (hydrolyzed/pre-condensed) silanes have the disadvantage that they can be too easily washed away from the surface in the subsequent rinsing stages, and therefore, their rust-protective effect is limited. Although this may be at least partially avoided in case of silanes, when silane-based treated surfaces are cured at comparably high temperatures, such a procedure is, however, not industrially viable, both from an economic and ecological point of view. As far as the use of molybdates is concerned, an additional disadvantage is that these may come under more environmental scrutiny in the coming years as well.
  • Silicates tend to inhibit the layer formation of film obtained after and during the chemical pretreatment if used at too high concentrations in the cleaning composition or in the rinsing composition and often lead to incrustations due to the formation of hardly soluble metal-silicate compounds under industrial production conditions, and are hence difficult to handle, which is disadvantageous as well.
  • Iron (III) cations containing alkaline cleaning compositions are known from, e.g., US 2014/023882 A1 , US 2013/202800 A1 and WO 2012/109339 A2, which result in the deposition of layers containing iron and iron oxides/hydroxides onto the metallic surfaces such as, e.g., zinc-coated substrates.
  • the newly formed iron containing layer is prone to rinse bath corrosion effects such as flash rusting, which makes their use disadvantageous.
  • nitrite/nitrate in the rinsing baths, as particularly nitrite may effectively prevent rinse bath corrosion due to its oxidizing properties.
  • nitrites have also come under scrutiny from a health perspective because they are toxic and hence require extensive labelling, which makes their use disadvantageous.
  • Other examples for use as additives in the rinsing compositions to be used are aromatic compounds that are known to show a relatively high tendency to deposit onto surfaces such as catechols (e.g., dopamines).
  • catechol-containing solutions such as dopamine-containing solutions
  • cleaning compositions prior to any chemical pretreatment
  • catechol-containing solutions such as dopamine-containing solutions
  • WO 2018/119373 A1 The use of catechol-containing solutions (such as dopamine-containing solutions) in cleaning compositions (prior to any chemical pretreatment) is, e.g., known from WO 2018/119373 A1.
  • the use of such organic aromatic compounds has the disadvantage that these are often not compatible with alkaline cleaning compositions due to uncontrollable polymerization, such that they cannot be used as additives in these compositions.
  • dopamine tends to polymerize uncontrollably in already slightly alkaline medium, it can potentially deposit in an inhomogeneous manner on the surface of the metal substrates and may affect subsequent chemical pretreatment such as conversion steps adversely, which makes their use disadvantageous.
  • a first subject-matter of the present invention is a method of cleaning of at least one metallic surface of at least one substrate, the method comprising at least step 1 ) and optionally also step 2), namely
  • aqueous alkaline composition AAC comprises besides water at least constituents a1 ) to a4), which are different from one of another, namely at least one alkalinity inducing source as constituent a1 ), at least one surfactant as constituent a2), optionally at least one complexing agent as optional constituent a3), and optionally at least one of phosphate anions, which optionally are condensed, and borate anions as optional constituent a4), and
  • aqueous rinsing composition ARC optionally rinsing the cleaned surface obtained after step 1 ) at least once with an aqueous rinsing composition ARC, characterized in that at least one of titanium, zirconium and hafnium cations is present, preferably zirconium cations, - when optional step 2) is not performed - as further constituent a5), being different from each of constituents a1 ) and a2) and optional constituents a3) and a4), in the aqueous alkaline composition AAC used in step 1 ) or is present - when optional step 2) is performed - as further constituent a5) in the aqueous alkaline composition AAC used in step 1 ) and/or as constituent in the aqueous rinsing composition ARC used in step 2).
  • a further subject-matter of the present invention is an aqueous cleaning composition AAC as defined hereinbefore and hereinafter and as used in step 1 ) of the cleaning method, which comprises besides water and constituents a1 ) and a2) and optional constituents a3) and/or a4) at least one of titanium, zirconium, and hafnium cations, preferably zirconium cations, as constituent a5).
  • a further subject-matter of the present invention is a concentrate, from which the inventive aqueous cleaning composition AAC is at least obtainable by dilution with water and, optionally, further, by pH adjustment.
  • a further subject-matter of the present invention is a method of chemical pretreatment of at least one cleaned metallic surface of at least one substrate, wherein cleaning of the at least one metallic surface has been carried out according to the cleaning method as defined hereinbefore and hereinafter, the method of chemical pretreatment further comprising at least step 3) and optionally one or more of steps 4) and 5), namely
  • aqueous, preferably acidic, composition AC being suitable to form a coating film, in particular a conversion coating film, at least in portion onto said cleaned and optionally rinsed surface, wherein the aqueous, preferably acidic, composition AC is different from both the aqueous alkaline composition AAC and from the aqueous rinsing composition ARC,
  • step 4) optionally rinsing the coating film obtained after step 3) at least once with an aqueous rinsing composition ARC2, which preferably consists or essentially consists of water only, and 5) optionally curing or drying the optionally rinsed coating film obtained after step
  • a further subject-matter of the present invention is a method of coating of at least one chemically pretreated metallic surface of at least one substrate, wherein chemical pretreatment of the at least one metallic surface has been carried out according to the wherein chemical pretreatment as defined hereinbefore and hereinafter, the method of coating further comprising at least step 6), namely
  • step 6) applying at least one coating material composition comprising at least one filmforming polymer and/or resin onto the optionally rinsed film obtained after step 3) or 4) or onto a dried or cured, preferably dried, film, which in turn is obtainable from drying or curing the film obtainable from optional step 5) as defined in connection with the chemical pretreatment as defined hereinbefore and hereinafter.
  • a further subject-matter of the present invention is a substrate, which is a cleaned substrate being obtainable by the cleaning method according to the present invention as defined hereinbefore and hereinafter, a chemically pretreated substrate being obtainable by the chemical pretreatment method according to the present invention as defined hereinbefore and hereinafter, or a coated substrate being obtainable by the coating method according to the present invention as defined hereinbefore and hereinafter.
  • the method according to the present invention and the cleaning composition according to the present invention are suitable for both effectively cleaning substrates having metallic surfaces and at the same time for effectively protecting the metallic surfaces of these substrates from rinse bath corrosion including protection from flash rust and avoidance of the occurrence of white spots. It has been in particular found that corrosion defects such as flash rusting on steel such as CRS or HRS and the formation of white spots on zinc-coated or zinc- containing substrates such as HDG, EG or ZM (steel being coated at least in portion with at least one kind of zinc-aluminum-magnesium alloy) can be entirely avoided or at least reduced to a great extent compared to conventional cleaning methods.
  • aqueous alkaline composition AAC used in step 1 which comprises zirconium cations as constituent a5)
  • AAC used in step 1 which comprises zirconium cations as constituent a5
  • applying the method according to the present invention and using the cleaning composition according to the present invention does not lead to the disadvantages observed, when using conventional cleaning compositions and conventional cleaning methods known in the prior art.
  • applying the method according to the present invention and using the cleaning composition according to the present invention does not lead to environmental and/or health concerns and/or economic disadvantages, in particular due to the constituents used for preparing the cleaning composition and the rinsing composition(s).
  • compositions comprising in the sense of the present invention, in connection for example with the aqueous alkaline composition AAC and/or the aqueous rinsing composition ARC or with the aqueous composition used for subsequent chemical pretreatment has the meaning of “consisting of’.
  • Consisting of e.g., to any of these compositions referred to hereinbefore, it is possible - in addition to all mandatory constituents present therein - for one or more of the further optional constituents identified hereinafter to be also included therein. All constituents may in each case be present in their preferred embodiments as identified below.
  • the cleaning method according to the present invention comprises at least step 1 ) and optionally also step 2).
  • the method may, however, comprise one or more further additional optional steps.
  • step 1 of the cleaning method at least one metallic surface of at least one substrate is contacted with composition AAC.
  • the term “metallic surface” in the sense of the present invention preferably means that the surface of the substrate used is at least partially made of at least one metal, i.e. , that at least one region of said surface is made of at least one metal and/or alloy thereof.
  • the surface can consist of different regions comprising different metals and/or alloys thereof.
  • the overall surface of the substrate is made of at least one metal and/or alloy thereof, more preferably, the whole substrate is made of at least one metal and/or alloy thereof, i.e. , the substrate consists of at least one metal and/or alloy thereof.
  • the substrate is an electrically conductive substrate, which is used customarily and known to the skilled person.
  • the metallic surface of the substrate can be made of any kinds of metals and/or alloys thereof.
  • the metal and/or alloy thereof is selected from the group consisting of steel, steel alloys, aluminum, aluminum alloys, zinc, zinc alloys such as zincmagnesium alloys and/or zinc-iron alloys, magnesium, magnesium alloys such as zincmagnesium alloys.
  • Steel and steel alloys are preferably selected from cold rolled steel (CRS), hot rolled steel (HRS), galvanized steel (zinc plated steel) such as hot-dip galvanized steel (hot zinc dipped steel; HDG) and electrolytical ly galvanized steel (EG), and steel coated at least in portion with at least one kind of zinc-aluminum- magnesium alloy (ZM), and mixtures thereof.
  • the at least one metallic surface of the at least one substrate is at least partially made of at least one kind of steel, said at least one kind of steel optionally containing zinc and/or at least one zinc alloy, and/or said at least one kind of steel being optionally coated at least in portion with at least one kind of zinc and/or zinc alloy including at least one kind of zinc-aluminum-magnesium alloy.
  • the geometry and shape of the substrate is not limited. Examples include strips, sheets, slugs, wires, and coils as well as parts of vehicles or vehicle bodies, which are, e.g., suitable for use in the automotive industry.
  • step 1 at least one surface of at least one substrate is contacted at least in portion with an aqueous alkaline composition AAC for cleaning the substrate.
  • cleaning of the portion of the surface is achieved.
  • the cleaning method including cleaning step 1 ) preferably represents part of a pretreatment.
  • pretreatment as used herein is preferably used in accordance with the term “surface pretreatment” as defined in Rdmpp Lexikon “Lacke und Druckmaschine” (Publisher: Ulrich Zorll, Editor: Hans-Jurgen P. Adler - Stuttgart; New York: Thieme, 1998; term: “Oberflachenvor harmony” page 417).
  • the first step(s) of a surface treatment is/are often one or more cleaning step(s) with aqueous or non-aqueous cleaning compositions (also called “surface preparation step”).
  • aqueous or non-aqueous cleaning compositions also called “surface preparation step”.
  • said step involves use of an aqueous alkaline cleaning composition AAC.
  • a pretreatment method according to the present invention hence, preferably encompasses the cleaning step 1 ) of the inventive method, which represents a surface preparing cleaning step, and which is different from, e.g., the chemical pretreatment step 3) and of the inventive chemical pretreatment method described hereinafter.
  • the term “at least in portion” preferably means in this context, in accordance with the general understanding of said term, that in some cases it might be desired or sufficient to contact not the whole surface of the substrate with the cleaning composition AAC. If only part of the surface is contacted with the composition, it is typically the same part for all steps of the method. However, generally, it is desired to contact the whole surface of the substrate.
  • the “contacting” according to step 1 ) can be, e.g., a spraying, a dipping or a roll coating step or any combination thereof.
  • the aqueous alkaline composition AAC can also be applied by flooding the surface or even manually by wiping or brushing. Preferred is spraying, dipping or roll coating or any combination thereof, most preferred is spraying or dipping, in particular spraying.
  • the treatment time i.e. , the period of time the surface is contacted with the aqueous alkaline composition AAC in step 1 ), is preferably from 15 seconds to 20 minutes, more preferably from 10 seconds to 10 minutes, and most preferably 30 seconds to 7.5 minutes, as for example 1 to 5 minutes.
  • contacting step 1 is performed by spraying, dipping or roll coating, more preferably by spraying or dipping, preferably for a period of >10 to 10 minutes, more preferably for a period of >30 seconds to 7.5 minutes, even more preferably for a period of 1 minute to 5 minutes.
  • Aqueous alkaline composition A AC used in step 1) Aqueous alkaline composition A AC used in step 1)
  • the aqueous alkaline composition AAC used in step 1 ) comprises besides water at least constituents a1 ) to a4), which are different from one of another, namely at least one alkalinity inducing source as constituent a1 ), at least one surfactant as constituent a2), optionally at least one complexing agent as optional constituent a3), and optionally at least one of phosphate anions, which optionally are condensed, and/or borate anions as optional constituent a4).
  • the aqueous alkaline composition AAC can be prepared from a concentrate containing at least constituents a1 ) and a2) and optional constituents a3) and/or a4) and optionally a5) by dilution of the concentrate with water.
  • optional rinsing step 2) When optional rinsing step 2) is not performed, at least one of titanium, zirconium, and hafnium cations, preferably zirconium cations, is further present in the aqueous alkaline composition AAC as additional constituent a5). Constituent a5) is different from each of constituents a1 ) to a4).
  • optional rinsing step 2) is performed, at least one of titanium, zirconium, and hafnium cations, preferably zirconium cations, is further present in the aqueous alkaline composition AAC used in step 1 ) as additional constituent a5) and/or is present as constituent in the aqueous rinsing composition ARC used in step 2).
  • the aqueous alkaline composition AAC used in step 1 has a pH value in a range of from >7.5 to ⁇ 12.5 or 7.5 to ⁇ 12.0, more preferably of from >7.5 to ⁇ 11 .5, still more preferably of from >8.0 to ⁇ 11.25, even more preferably of from >8.5 to ⁇ 11.0, still more preferably of from >9.0 to ⁇ 1 1 .0, yet more preferably of from >9.5 to ⁇ 11.0.
  • the pH value is measured at 55 °C.
  • the pH value can be in particular adjusted by using constituent a1 ), in particular sodium and/or potassium hydroxide and/or carbonate, for alkaline adjustment, and can be in particular adjusted in case acidic adjustment is needed by at least one inorganic acid such as phosphoric and/or boric acid.
  • constituent a1 in particular sodium and/or potassium hydroxide and/or carbonate, for alkaline adjustment, and can be in particular adjusted in case acidic adjustment is needed by at least one inorganic acid such as phosphoric and/or boric acid.
  • aqueous with respect to the aqueous composition used in step 1 ) in the sense of the present invention preferably means that the composition is a composition containing at least 50 wt.-%, preferably at least 60 wt.-%, more preferably at least 70 wt.-% in particular at least 80 wt.-%, most preferably at least 90 wt.-% of water, based on its total content of organic and inorganic solvents including water.
  • the aqueous composition may contain at least one organic solvent besides water - however, in an amount lower than the amount of water present.
  • the aqueous composition contains at least 50 wt.-%, preferably at least 60 wt.-%, more preferably at least 70 wt.-% in particular at least 80 wt.-%, most preferably at least 90 wt.-% of water, in each case based on its total weight.
  • the aqueous alkaline composition AAC used in step 1 has a temperature in a range of from 30 to 75 °C, more preferably of from 35 to 70 °C, still more preferably of from 40 to 65 °C, yet more preferably of from 45 to 60 °C.
  • the aqueous alkaline composition AAC can be a dispersion or solution. Preferably, it is a solution.
  • the aqueous alkaline composition AAC used in step 1 ) is free or essentially free of fluorides, preferably is free of fluorides or comprises a maximum amount of fluorides of ⁇ 10 mg/L, calculated as fluorine (F), and/or is free or essentially free of molybdenum cations, preferably is free of molybdenum cations or comprises a maximum amount of molybdenum cations of ⁇ 10 mg/L, calculated as metal, and/or is free or essentially free of organosilanes and/or hydrolysis and/or condensation products thereof, preferably is free of organosilanes and/or hydrolysis and/or condensation products thereof or comprises a maximum amount of organosilanes and/or hydrolysis and/or condensation products thereof of ⁇ 10 mg/L, calculated as Si, and/or is free or essentially free of iron cations, in particular iron (III) cations, preferably is free of iron cations or comprises a maximum amount of iron cations, in
  • the aqueous alkaline composition AAC used in step 1 ) is free or essentially free of silicates, preferably is free of silicates or comprises a maximum amount of silicates of ⁇ 100 ppm, more preferably of ⁇ 20 ppm, calculated as SiC>2, and/or is free or essentially free of borate anions, preferably is free of borate anions or comprises a maximum amount of borate anions of ⁇ 10 mg/L, calculated as boron.
  • Essentially free in this context means in each case that at least on purpose none of the aforementioned constituents is added, but it may not be ruled out that any residues of any of the constituents may be present as impurities and/or may be present in amounts being naturally present in water.
  • At least one alkalinity inducing source is used as constituent a1 ).
  • alkalinity inducing sources in particular anion sources
  • at least one hydroxide anion and/or carbonate anion source preferably a metal salt such as sodium and/or potassium hydroxide and/or carbonate, in particular potassium hydroxide and/or carbonate, is used for preparing the aqueous alkaline composition AAC.
  • the aqueous alkaline composition AAC comprises preferably hydroxide and/or carbonate anions as constituent a1 ).
  • the aqueous alkaline composition AAC comprises the at least one alkalinity inducing source present as constituent a1 ) in an amount such that the required alkalinity is met.
  • at least one alkalinity inducing source being present as constituent a1 ) is present in an amount in a range of from 0.2 to 40 g/L, more preferably of from 0.5 to 30 g/L, even more preferably of from 1 .0 to 25 g/L, even more preferably of from 3.0 to 15 g/L.
  • the aqueous alkaline composition AAC can be prepared from a concentrate by dilution of the concentrate with water.
  • the concentrate comprises the at least one alkalinity inducing source present as constituent a1 ) in the composition in an amount of from 5 to 500 g/L, more preferably of from 10 to 250 g/L, even more preferably of from 20 to 100 g/L.
  • At least one surfactant is used as constituent a2).
  • surfactant surface active agent
  • tenside as defined in Rdmpp Lexikon “Lacke und Druckmaschine” (Publisher: Ulrich Zorll, Editor: Hans-Jurgen P. Adler - Stuttgart; New York: Thieme, 1998; term: “tenside” pages 557 and 558).
  • Suitable surfactants are known to a person skilled in the art and, e.g., disclosed in WO 2020/200838 A1 .
  • the at least one surfactant is selected from non-ionic, anionic and/or cationic surfactants, most preferably from non-ionic surfactants.
  • Suitable non-ionic surfactants include in particular alkylphenol alkoxylates, especially alkylphenol ethoxylates, having Cs to C14 alkyl chains and a degree of alkoxylation of 5 to 30 mol per mole of phenol, alkylpolyglucosides having an alkyl chain length of Cs to C22, preferably C to C1 s, and containing 1 to 20, preferably 1 to 5, glucoside units, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates, N-alkylglucamides or else block copolymers consisting of ethylene oxide, propylene oxide and/or butylene oxide, and alkoxylated Cs to C22 alcohols such as fatty alcohol alkoxylates, oxoprocess alcohol alkoxylates and Guerbet alcohol alkoxylates, where the alkoxylation may take place with ethylene oxide, propylene oxide, butylene oxide and/or a mixture of these, as
  • the alcohols preferably have 8 to 18 carbon atoms; the degree of alkoxylation ranges typically between 2 to 50 mol, preferably 3 to 20 mol, of at least one of the stated alkylene oxides per mole of alcohol.
  • the alkylene oxide head group may additionally contain the following so-called endcapping groups as a modification: benzyl, methyl and/or tert-butyl capping.
  • anionic surfactants in particular can be used: fatty alcohol sulfates having alkyl chain lengths of 8 to 22, preferably 10 to 18, carbon atoms, for example lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate or stearyl sulfate, alkyl ether sulfates having alkyl chain lengths of 8 to 22, preferably 10 to 18, carbon atoms, and linear Cs to C20 alkylbenzenesulfonates or else alkanesulfonates and soaps, such as sodium or potassium salts of Cs to C24 carboxylic acids.
  • Cationic surfactants employed, depending on application, are in particular quaternary mono- and di-(C?-C25 alkyl)dimethylammonium compounds, ester quats, especially quaternary esterified mono-, di- and trialkanolamines esterified with C8-C22 carboxylic acids, and C7 to C25 alkylamines, N,N-dimethyl-N-(hydroxy-C7-C25 alkyl)ammonium salts and/or imidazoline quats.
  • the at least one surfactant preferably is at least one nonionic surfactant.
  • the foaming tendency of anionic surfactants is too high, while cationic surfactants often attach to the metallic surface, and may consequently give rise to problems within the deposition of conversion coating films to be subsequently applied.
  • the aqueous alkaline composition AAC comprises the at least one surfactant as the at least one constituent a2) in an amount of from 0.3 to 10.0 g/L, more preferably of from 0.4 to 5.0 g/L, even more preferably of from 0.5 to 3.5 g/L.
  • the at least one surfactant being present as constituent a2) is selected from non-ionic, anionic and/or cationic surfactants, preferably from non-ionic surfactants, and/or the at least one surfactant being present as constituent a3) is present in an amount in a range of from 0.3 to 10.0 g/L, preferably of from 0.4 to 5.0 g/L, even more preferably of from 0.5 to 3.5 g/L.
  • Optional constituent a3) At least one complexing agent is optionally used as optional constituent a3).
  • Suitable complexing agents are known to a person skilled in the art.
  • the at least one complexing agent being optionally present as constituent a3) is selected from (i) carboxylic acids, salts thereof, derivatives, in particular esters, thereof, and mixtures thereof, wherein the carboxylic acids include polymeric carboxylic acids in each case, (ii) sulfamic acids, (iii) phosphonic acid, phosphonates and derivatives of phosphonic acid such as esters thereof, (iv) polyols, in particular having two or more OH-groups, wherein the polyols include polymeric polyols, and (v) polyethyleneimines, and mixtures of (i) to (v).
  • carboxylic acids include polymeric carboxylic acids in each case, (ii) sulfamic acids, (iii) phosphonic acid, phosphonates and derivatives of phosphonic acid such as esters thereof, (iv) polyols, in particular having two or more OH-groups, wherein the polyols include polymeric polyols, and
  • the at least one complexing agent being optionally present as at least one optional constituent a3) is selected from (i) carboxylic acids, salts thereof, derivatives, in particular esters, thereof, and mixtures thereof, wherein the carboxylic acids include polymeric carboxylic acids in each case, (iii) phosphonic acid, phosphonates and derivatives of phosphonic acid such as esters thereof, and mixtures thereof.
  • the at least one complexing agent being optionally present as at least one optional constituent a3) is selected from (i) carboxylic acids, salts thereof, derivatives, in particular esters, thereof, and mixtures thereof, wherein the carboxylic acids include polymeric carboxylic acids in each case.
  • Exemplary suitable complexing agents are HEDP (1 -hydroxyethylidene- 1 ,1 -diphosphonic acid), EDTMP (ethylenediamine tetra(methylene phosphonic acid), MGDA-Na3 (methylglycinediacetic acid trisodium salt), DTPA-Na5 (diethylenetriaminepentaacetic acid pentasodium salt), PBTC-Na4 (2- phosphonobutane-1 ,2, 4, -tricarboxylic acid tetrasodium salt), polyethyleneimines, amido sulfonic acid, and mixtures thereof.
  • the at least one complexing agent being optionally present as constituent a3) is present in an amount in a range of from 0 or 0.2 to 10 g/L, preferably of from 0 or 0.2 or 0.5 to 5 g/L, more preferably of from 0 or 0.5 to 3 g/L.
  • phosphate anions which optionally are condensed, and borate anions are present as optional constituent a4). If phosphate anions are present, these can be hence present in a condensed form such as in case of pyrophosphates (diphosphates) and/or in a non-condensed form. In other words, mixtures of both forms can also be present.
  • phosphates includes polyphosphates as well such as tripolyphosphates.
  • the at least one of phosphate anions and borate anions are selected from preferably both condensed (such as diphosphate anions) and non-condensed phosphate anions.
  • the at least one of phosphate anions and borate anions, preferably phosphate anions, being optionally present as optional constituent a4), wherein the phosphate anions are optionally are condensed, being optionally present as constituent a4) are selected from both condensed and non-condensed phosphate anions including polyphosphate anions, and/or the at least one of phosphate anions and borate anions, preferably phosphate anions, wherein the phosphate anions are optionally condensed, being optionally present as optional constituent a4), are present as optional constituent a4) in an amount of from 0 or 0.5 g/L to 10 g/L, preferably of from 0 or 1 .0 to 8 g/L, calculated as P2O5 or as B2O3.
  • At least one of titanium, zirconium, and hafnium cations, preferably zirconium cations, may further be present in the aqueous alkaline composition AAC.
  • constituent a5) is necessarily present in composition AAC.
  • constituent a5) may be present in composition AAC, but does not have to be, since in this case it is possible that at least one of titanium, zirconium, and hafnium cations, preferably zirconium cations, is merely present in the aqueous rinsing composition ARC used in step 2).
  • the aqueous rinsing composition ARC when at least one of titanium, zirconium and hafnium cations is present in the aqueous rinsing composition ARC as constituent, none of titanium, zirconium and hafnium cations is present in the aqueous alkaline composition AAC as constituent a5).
  • at least one of titanium, zirconium, and hafnium cations, more preferably zirconium cations, is present as constituent a5) in the aqueous alkaline composition AAC used in step 1 ).
  • none of titanium and hafnium cations are present in the composition AAC.
  • titanium, zirconium, and hafnium cations more preferably at least one of titanium and zirconium cations, even more preferably zirconium cations, is present as constituent a5) in the aqueous alkaline composition AAC, which is preferred, it is preferably present in an amount in a range of from >0.1 to ⁇ 3000 mg/L, preferably of from >1 to ⁇ 1000 mg/L, more preferably of from >5 to ⁇ 500 mg/L, yet more preferably of from >10 to ⁇ 200 mg/L, calculated in each case as metal.
  • composition AAC Preferably, no fluoride anions containing precursor has been used for generation of the titanium, zirconium, and hafnium cations present as constituent a5) in composition AAC. If fluoride anions containing precursors such as hexafluorozirconic acid are used, undesired precipitation may occur due to the alkaline conditions present in composition AAC. More preferably, the aqueous alkaline composition AAC used in step 1 ) is free or essentially free of fluoride anions.
  • the at least one of titanium, zirconium and hafnium cations are present and/or can be incorporated in the aqueous alkaline composition AAC used in step 1 ) in a complexed form such as chelated form, which is stable in alkaline medium.
  • stable in alkaline medium in this context preferably means that no precipitation takes place in alkaline medium and in particular under the alkaline conditions, which are present in composition AAC.
  • At least one alcohol more preferably at least one C3- to Cs-alcohol such as at least one C4-alcohol, e.g., n-butanol and/or tert.- butanol, and/or at least one organic acid, which optionally is OH-functional, preferably at least one C3- to Cs-carboxylic acid, is used for generating the complexes such as chelates of at least one of titanium, zirconium, and hafnium cations, which are present and/or can be incorporated in the aqueous alkaline composition AAC.
  • the complexes such as chelates of at least one of titanium, zirconium, and hafnium cations, which are present and/or can be incorporated in the aqueous alkaline composition AAC.
  • Such complexes are commercially available, e.g., in the form of the products of the Tyzor® series such as Tyzor® 212 and Tyzor® 223 of the company Dorf Ketal.
  • a metalate of at least one of titanium, zirconium and hafnium cations such as at least one zirconate and/or titanate can be used.
  • a metal alkoxide the metal of the metal alkoxide being selected from Ti, Zr and/or Hf, is used.
  • each alkoxide group has 3 to 8, more preferably 3 to 6, even more preferably 3 to 4 carbon atoms.
  • the at least one of titanium, zirconium and hafnium cations has/have been generated by incorporation of at least one carbonate of titanium, zirconium and/or hafnium into the aqueous alkaline composition AAC, even more preferably by incorporation of at least one alkali, earth alkali, and/or ammonium carbonate of titanium, zirconium and/or hafnium, still more preferably of at least one alkali and/or ammonium carbonate of titanium and/or zirconium.
  • the aqueous alkaline composition AAC comprises at least one solubilizer as optional constituent a6), which is used an auxiliary additive for keeping the at least one surfactant a3) in solution within the composition.
  • suitable solubilizers are alkali metal salts of carboxylic acids such as such as potassium octanoate.
  • the at least one optional constituent a6) is present in the composition in an amount of from 0.2 to 6.0 g/L, more preferably of from 0.3 to 5.0 g/L, even more preferably of from 0.5 to 4.0 g/L.
  • step 2) the cleaned surface obtained after step 1 ) is rinsed at least once with an aqueous rinsing composition ARC.
  • step 2) is performed.
  • step 2 at least one of titanium, zirconium and hafnium cations is present in the aqueous alkaline composition AAC used in step 1 ) as additional constituent a5) and/or is present as constituent in the aqueous rinsing composition ARC used in step 2).
  • the aqueous rinsing composition ARC preferably consists or essentially consists of water.
  • titanium, zirconium, and hafnium cations are present as constituent in the aqueous rinsing composition ARC, it is preferably present in an amount in a range of from >0.1 to ⁇ 3000 mg/L, preferably of from >1 to ⁇ 1000 mg/L, more preferably of from >5 to ⁇ 500 mg/L, yet more preferably of from >10 to ⁇ 200 mg/L, calculated in each case as metal.
  • none of titanium and hafnium cations are present in the composition ARC. If at all, only zirconium cations are preferably present in composition ARC.
  • composition ARC used in optional step 2) is free or essentially free of fluoride anions.
  • aqueous rinsing composition ARC Preferably, in case at least one of titanium, zirconium, and hafnium cations are present in the aqueous rinsing composition ARC, the same precursors and/or constituents can be used, which have been described hereinbefore in connection with constituent a5).
  • At least one of titanium, zirconium, and hafnium cations can be present in composition ARC used in optional step 2) in a complexed form, which is stable in alkaline medium, more preferably the at least one of titanium, zirconium and hafnium cations has/have been generated by incorporation of at least one carbonate of titanium, zirconium and/or hafnium into the aqueous rinsing composition ARC, even more preferably by incorporation of at least one alkali, earth alkali, and/or ammonium carbonate of titanium, zirconium and/or hafnium, still more preferably of at least one alkali and/or ammonium carbonate of titanium and/or zirconium.
  • the aqueous rinsing composition ARC used in optional step 2) is free or essentially free of fluorides, preferably is free of fluorides or comprises a maximum amount of fluorides of ⁇ 10 mg/L, calculated as fluorine (F), and/or is free or essentially free of molybdenum cations, preferably is free of molybdenum cations or comprises a maximum amount of molybdenum cations of ⁇ 10 mg/L, calculated as metal, and/or is free or essentially free of organosilanes and/or hydrolysis and/or condensation products thereof, preferably is free of organosilanes and/or hydrolysis and/or condensation products thereof or comprises a maximum amount of organosilanes and/or hydrolysis and/or condensation products thereof of ⁇ 10 mg/L, calculated as Si, and/or is free or essentially free of iron cations, in particular iron (III) cations, preferably is free of iron cations or comprises a maximum amount of iron cations or
  • the aqueous rinsing composition ARC used in optional step 2) is free or essentially free of silicates, preferably is free of silicates or comprises a maximum amount of silicates of ⁇ 100 ppm, more preferably of ⁇ 20 ppm, calculated as SiC>2, and/or is free or essentially free of borate anions, preferably is free of borate anions or comprises a maximum amount of borate anions of ⁇ 10 mg/L, calculated as boron.
  • the aqueous rinsing composition ARC consists or essentially consists of water. Tap water and/or deionized water can be used for rinsing.
  • step 2) can be performed more than once. It is hence possible, e.g., to perform a rinsing in step 2) once with tap water followed by rinsing with deionized water or vice versa.
  • composition AAC does not comprise constituent a5)
  • at least the first rinsing composition ARC used (after having performed cleaning step 1 )) comprises at least one of titanium, zirconium, and hafnium cations as constituent.
  • the second rinsing composition ARC used can be different from or identical to the first rinsing composition used.
  • it preferably consists or essentially consists of water, in particular when the first rinsing composition ARC used comprises at least one of titanium, zirconium, and hafnium cations as constituent.
  • step 1 Following step 1 ) and optionally step 2) one or more of the following optional steps can be performed in this order:
  • Step A-1 subjecting the surface of the substrate to acidic or alkaline pickling, i.e., etching, and subsequently rinsing the surface of the substrate,
  • Step B-1 contacting the surface of the substrate with an aqueous composition comprising at least one mineral acid, said aqueous composition being different from the aqueous alkaline composition AAC used in step 1 ) and from the aqueous composition AC used in step 3) and from composition ARC used in optional step 2), and
  • Step C-1 rinsing the surface of the substrate obtained after the contact according to step A-1 ) and/or B-1 ).
  • Optional step B-1 ) preferably serves to remove oxides, undesired alloy components, the skin, brushing dust etc. from the surface of the substrate and to activate the surface thereby further for the subsequent chemical pretreatment in step 3).
  • the at least one mineral acid of the composition in step B-1 ) is sulfuric acid, phosphoric acid and/or nitric acid, more preferably sulfuric acid.
  • Rinsing step C-1 ) and the optional rinsing step 2) are preferably performed by using deionized water or tap water.
  • Aqueous alkaline composition AAC AAC
  • a further subject-matter of the present invention is an aqueous cleaning composition AAC as defined hereinbefore and hereinafter and as used in step 1 ) of the cleaning method, which comprises besides water and constituents a1 ) and a2) and optionally a3 and/or a-4), at least one of titanium, zirconium, and hafnium cations, preferably zirconium cations, as constituent a5).
  • a further subject-matter of the present invention is a concentrate, from which the inventive aqueous cleaning composition AAC is at least obtainable by dilution with water and, optionally, further, by pH adjustment.
  • the concentrate thus preferably represents a master batch for producing the aqueous composition AAC.
  • the concentrate used to produce the aqueous alkaline composition AAC typically contains the constituents of the aqueous alkaline composition AAC to be produced in the desired proportions, but at a higher concentration. Such concentrate is diluted with water to the desired concentrations of the constituents as disclosed hereinbefore to form composition AAC. If necessary, the pH value of the composition may be adjusted after dilution as well as outlined hereinbefore. Of course, it is also possible to further add any of the optional constituents of the composition to the water used for dilution or to add any of the optional or some of the necessary constituents after diluting the concentrate with water. It is, however, preferred that the concentrate already contains all necessary constituents.
  • the aqueous alkaline composition AAC is obtainable from a concentrate by dilution with water, preferably with deionized water, such that the concentrate is present in the composition after dilution in an amount of from 5 to 60 g/L, more preferably 10 to 40 g/L, even more preferably of from 15 to 30 g/L, based on the total weight of the composition (obtained after dilution of the concentrate).
  • the concentrate is diluted with water in a weight ratio of 1 :5000 to 1 :10, more preferred 1 : 1000 to 1 : 10, most preferred in a ratio of 1 :300 to 1 : 10 and even more preferred 1 : 150 to 1 :50 to produce the composition AAC.
  • composition AAC can be prepared from a concentrate by dilution of the concentrate with water.
  • the concentrate comprises the at least one alkalinity inducing source present as constituent a1 ) in the final composition AAC in an amount of from 5 to 500 g/L, more preferably of from 10 to 250 g/L, even more preferably of from 20 to 100 g/L, the at least one complexing agent being optionally present as optional constituent a3) in the final composition AAC in an amount of from 0 or 5 to 200 g/L, more preferably of from 0 or 7.5 to 150 g/L, even more preferably of from 0 or 10 to 100 g/L, and optionally phosphate anions, which optionally are condensed, being optionally present as optional constituent a4) in the final composition AAC, in an amount of from 0 or 5 to 250 g/L, more preferably of from 0 or 10 to 150 g/L, even more preferably of from 0 or 25 to 100 g/L, in each case calculated as P2O5, and/or optionally borate anions, being optionally present as optional constituent
  • the concentrate in particular in case it is a 1 K product, further preferably already comprises the at least one surfactant being present as constituent a2) in the final composition AAC, preferably in an amount of from 1 to 100 g/L, more preferably of from 2.5 to 75 g/L, even more preferably of from 5 to 50 g/L.
  • the concentrate in particular in case it is a 2K or even 3K product, preferably not yet comprises the at least one surfactant being present as constituent a2) in the final composition AAC, but rather is this constituent added as a separate component only at a later stage, when composition AAC is obtainable from the concentrate by dilution with water and, optionally, further, by pH adjustment.
  • the at least one surfactant being present as constituent a2) in the final composition AAC is added as a separate component during the process of preparing composition AAC in an amount such that it is preferably present in the final composition AAC in an amount of from 0.3 to 10.0 g/L, more preferably of from 0.4 to 5.0 g/L, even more preferably of from 0.5 to 3.5 g/L.
  • the concentrate in particular in case it is a 1 K product, further preferably already comprises the at least one of titanium, zirconium and hafnium cations being present as constituent a5) in the final composition AAC, preferably in an amount of from 2 to 150 g/L, more preferably of from 5 to 100 g/L, even more preferably of from 10 to 50 g/L, calculated in each case as metal.
  • the concentrate in particular in case it is a 2K or even 3K product, preferably not yet comprises the at least one of titanium, zirconium and hafnium cations being present as constituent a5) in the final composition AAC, but rather is this constituent added as a separate component only at a later stage, when composition AAC is obtainable from the concentrate by dilution with water and, optionally, further, by pH adjustment.
  • the at least one of titanium, zirconium and hafnium cations being present as constituent a5) in the final composition AAC is added as a separate component during the process of preparing composition AAC in an amount such that it is preferably present in the final composition AAC in an amount of from >0.1 to ⁇ 3000 mg/L, more preferably of from >1 to ⁇ 1000 mg/L, still more preferably of from >5 to ⁇ 500 mg/L, yet more preferably of from >10 to ⁇ 200 mg/L, calculated in each case as metal.
  • the aqueous alkaline composition AAC is obtainable from a concentrate by dilution with water, preferably with deionized water, wherein the concentrate, i.e. , prior to dilution, comprises besides water at least one alkalinity inducing source, preferably hydroxide and/or carbonate anions, in particular carbonate anions, which is in turn obtainable from incorporation of a suitable metal salt such as sodium and/or potassium hydroxide and/or carbonate, in particular potassium carbonate, in an amount in a range of from 5 to 25 wt.-%, into the concentrate, based on the total weight of the concentrate, optionally at least one complexing agent, which is preferably selected from carboxylic acids, salts thereof, derivatives, in particular esters, thereof, and mixtures thereof, wherein the carboxylic acids include polymeric carboxylic acids in each case, in an amount in a range of from 0 or 1 to 5 wt.-%, based on the total weight of the concentrate, at least
  • the method of chemical pretreatment according to the present invention comprises at least step 3) and optionally one or more of steps 4) and 5) and is performed after having carried out the inventive cleaning method as defined hereinbefore and hereinafter.
  • the method of chemical pretreatment may, however, comprise one or more further additional optional steps.
  • chemical pretreatment is used in accordance with EN ISO 4618:2006 (E/F/D) (term: 2.41 “chemical pre-treatment”), which represents any chemical process applied to a surface prior to the application of a coating material.
  • treatments like chromatizing and phosphatizing and oxalating which can be subsumed under the term “conversion treatment” belong to the chemical pretreatment and thus are to be distinguished from (subsequent) coating steps, wherein coating materials, i.e., coating compositions such as powder coating compositions, electrodeposition coating compositions, aqueous or non-aqueous liquid coating materials are applied.
  • the chemical surface pretreatment may be achieved with passivation compositions and thin-film forming compositions in general, including aqueous compositions such as the composition, which is mandatorily used as chemical pretreatment composition in step 3).
  • step 3) the at least one cleaned and optionally rinsed surface of the at least one substrate (obtained after step 1 ) or after step 2) of the cleaning method) is contacted at least in portion with an aqueous, preferably acidic, composition AC being suitable to form a coating film, in particular a conversion coating film, at least in portion onto said cleaned and optionally rinsed surface.
  • the aqueous composition AC used in step 3) represents a chemical pretreatment composition.
  • the term “at least in portion” preferably means in this context, in accordance with the general understanding of said term, that in some cases it might be desired or sufficient to contact not the whole surface of the substrate with the chemical pretreatment composition. If only part of the surface is contacted with the composition, it is typically the same part for all steps of the method. However, generally, it is desired to contact the whole surface of the substrate.
  • the “contacting” according to step 3) can be a spraying, a dipping or a roll coating step or any combination thereof.
  • the aqueous composition can also be applied by flooding the surface or even manually by wiping or brushing. Preferred is spraying, dipping or roll coating, or any combination thereof.
  • the treatment time i.e. , the period of time the surface is contacted with the aqueous composition in step 3
  • the temperature of the aqueous composition used in step 3) is preferably of from 5 to 50 °C, more preferably of from 15 to 45 °C and most preferably from 25 to 40 °C.
  • the coating film formed in step 3) is a conversion coating film.
  • the aqueous coating composition AC is a conversion coating composition (or conversion treatment composition).
  • conversion treatment composition defines, in accordance with the general understanding of said term, a composition, which, if applied to a substrate metal produces a superficial layer containing a compound of the substrate metal (often referred to as conversion coating) and an anion of an environment (ISO 2080:2008 (E/F), term: 2.3 “conversion treatment”).
  • Aqueous composition AC used in step 3 3)
  • the aqueous, preferably acidic, composition AC used in step 3) is different from both the aqueous alkaline composition AAC and from the aqueous rinsing composition ARC.
  • aqueous with respect to the aqueous composition AC used in step 3) in the sense of the present invention preferably means that the composition is a composition containing at least 50 wt.-%, preferably at least 60 wt.-%, more preferably at least 70 wt.-% in particular at least 80 wt.-%, most preferably at least 90 wt.-% of water, based on its total content of organic and inorganic solvents including water.
  • the aqueous composition may contain at least one organic solvent besides water - however, in an amount lower than the amount of water present.
  • the aqueous composition contains at least 50 wt.-%, preferably at least 60 wt.-%, more preferably at least 70 wt.-% in particular at least 80 wt.-%, most preferably at least 90 wt.-% of water, in each case based on its total weight.
  • the aqueous composition AC used in step 3) is acidic.
  • the acidic aqueous composition preferably has a pH value in a range of from 0.5 to 6.5.
  • the pH value is measured at operating temperature.
  • the pH value of the acidic aqueous composition is more preferably in the range of from 1.0 to 6.0, still more preferably of from 2.0 or 3.0 to 5.5.
  • the pH can be preferably adjusted by using nitric acid, aqueous ammonia and/or sodium carbonate if necessary.
  • the total amount of all components (constituents) being present in the aqueous composition AC used in step 3) adds up to 100 wt.-%.
  • the aqueous composition can be a dispersion or solution. Preferably, it is a solution.
  • the aqueous composition AC used in step 3) of the chemical pretreatment method does not contain chromium ions such as Cr(VI) ions and/or Cr(lll) ions.
  • the aqueous composition AC used in step 3) may comprise at least one of oxalate and phosphate anions, in particular when it is acidic.
  • the aqueous composition AC comprises fluoride anions in an amount in a range of from 10 to 2000 mg/L, more preferably of from 15 to 1500 mg/L, even more preferably of from 20 to 1000 mg/L, still more preferably of from 25 to 500 mg/L, yet more preferably of from 25 to 500 mg/L, in each case calculated as fluorine.
  • fluoride anions such as complexes of zirconium, titanium and/or hafnium formed with fluoride ions are present in the composition, e.g., by coordination of fluoride anions to zirconium, titanium and/or hafnium cations in the presence of water.
  • fluoride anions may be generated by adding other water-soluble fluorine compounds, e.g., fluorides (other than complex fluorides of Ti, Zr and/or Hf) as well as hydrofluoric acid to the composition.
  • fluoride anions may be generated by adding other water-soluble fluorine compounds, e.g., fluorides (other than complex fluorides of Ti, Zr and/or Hf) as well as hydrofluoric acid to the composition.
  • fluoride anions may be generated by adding other water-soluble fluorine compounds, e.g., fluorides (other than complex fluorides of Ti, Zr and/or Hf) as well as hydrofluoric acid to the composition.
  • the free fluoride content is determined by means of a fluoride ion sensitive electrode according to the method disclosed in the ‘methods’ section.
  • the aqueous composition AC comprises at least one metal cation selected from the group consisting of titanium, zirconium and hafnium ions, and mixtures thereof, more preferably selected from the group of titanium and zirconium ions and mixtures thereof, even more preferably selected from zirconium ions.
  • the aqueous composition comprises at least one metal cation selected from the group consisting of titanium, zirconium and hafnium ions, and mixtures thereof, in an amount in a range of from 5 to 2000 mg/L, more preferably of from 7.5 to 1500 mg/L, even more preferably of from 10 to 1000 mg/L, still more preferably of from 15 to 500 mg/L, yet more preferably of from 20 to 300 mg/L, in each case calculated as metal.
  • a precursor metal compound is used to generate the at least one metal cation.
  • the precursor metal compound is water-soluble. Solubility is determined at a temperature of 20°C and atmospheric pressure (1.013 bar).
  • zirconium, titanium and/or hafnium compounds are the complex fluorides of these metals.
  • complex fluoride includes the single and multiple protonated forms as well as the deprotonated forms. It is also possible to use mixtures of such complex fluorides.
  • Complex fluorides in the sense of the present invention are complexes of zirconium, titanium and/or hafnium formed with fluoride ions in the composition, e.g., by coordination of fluoride anions to zirconium, titanium and/or hafnium cations in the presence of water.
  • the content of the at least one metal cation can be monitored and determined by the means of ICP-OES (optical emission spectroscopy with inductively coupled plasma). Said method is described hereinafter in the ‘method’ section.
  • the aqueous composition AC comprises at least one organosilane, preferably in an amount of from 5 to 1000 mg/L, more preferably of from 5 to 500 mg/L.
  • organosilane preferably in an amount of from 5 to 1000 mg/L, more preferably of from 5 to 500 mg/L.
  • examples are, e.g., (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)triethoxysilane, (3-glycidyloxypropyl)trimethoxysilane and/or (3- glycidyloxypropyl)triethoxysilane, and/or vinyltrimethoxysilane.
  • the at least one organosilane is present therein in a
  • the aqueous, preferably acidic, coating composition, in particular conversion coating composition used in step 3) comprises at least one metal cation selected from the group of titanium, zirconium, hafnium ions, and mixtures thereof, fluoride anions, and optionally at least one organosilane and/or at least one hydrolysis and/or condensation product thereof.
  • the aqueous composition AC may comprise further constituents such as other metal cations (other than Zr, Ti and/or Hf) such as Cu cations, and/or at least one water-soluble polymer such as a water-soluble polymer having least one kind of functional groups selected from acid groups, hydroxyl groups, and mixtures thereof. Solubility is determined at a temperature of 20°C and atmospheric pressure (1.013 bar).
  • the at least one water-soluble polymer is a homopolymer or copolymer obtainable from polymerization of at least one kind of ethylenically unsaturated monomers, wherein at least part of said monomers bear at least one kind of functional groups selected from acid groups, hydroxyl groups, and mixtures thereof, more preferably is a homopolymer or copolymer obtainable from polymerization of at least one kind of vinyl monomers and/or (meth)acrylic monomers, wherein at least part of said monomers bear at least one kind of functional groups selected from acid groups, hydroxyl groups, and mixtures thereof.
  • a conversion layer formed after drying or curing, preferably drying, the film obtainable after step 3), has a coating weight determined by XRF (X-ray fluorescence spectroscopy) of: 0.5 to 500 mg/m 2 , more preferably 1 to 400 mg/m 2 , even more preferably 3 to 350 mg/m 2 , still more preferably 5 to 300 mg/m 2 , of zirconium, titanium and/or hafnium ions, preferably of zirconium and/or titanium, in particular of zirconium, each calculated as metal.
  • XRF X-ray fluorescence spectroscopy
  • the cleaned surface obtained after step 1 ) is rinsed at least once with an aqueous rinsing composition ARC2, which preferably consists or essentially consists of water only.
  • Composition ARC2 may be and preferably is identical to aqueous rinsing composition ARC used in optional step 2) in case none of titanium, zirconium and hafnium cations is present in composition ARC.
  • Tap water and/or deionized water, preferably deionized water can be used for rinsing in optional step 4).
  • step 4) can be performed more than once. It is hence possible, e.g., to perform a rinsing in step 4) once with tap water followed by rinsing with deionized water or vice versa.
  • the optionally rinsed coating film obtained after step 3) or 4) is dried or cured to give a cured or dried coating layer, wherein the obtained cured or dried coating layer preferably has a dry film thickness below 0.5 pm.
  • the optional drying or curing step 5) may be preferably performed, e.g., at a temperature in the range of 15°C to 100°C, more preferably at a temperature in the range of 18°C to 95°C, in particular at a temperature in the range of 20°C to 90°C.
  • “Drying” in the sense of the present invention means physical drying by evaporation of in particular water originally present in the composition(s) used, whereas “curing” further includes a chemical reaction between at least two constituents originally present in the composition(s) and/or between at least one constituent originally present in the composition(s) and a suitable functional group present on the metallic surface or in the conversion film, e.g., in case a water-soluble polymer was present in the aqueous composition.
  • the obtained cured or dried coating layer obtained after step 4) has a dry film thickness in a range of from 1 nm to ⁇ 500 nm, more preferably of from 10 nm to 250 nm, in particular of from 80 to 150 nm.
  • the method of coating according to the present invention comprises at least step 6)) and is performed after having carried out the inventive chemical pretreatment method as defined hereinbefore and hereinafter.
  • the method of coating may, however, comprise one or more further additional optional steps.
  • step 6) at least one coating material composition comprising at least one film-forming polymer and/or resin is applied onto the optionally rinsed film obtained after step 3) or 4) or onto a dried or cured, preferably dried, film, which in turn is obtainable from drying or curing the film obtainable from optional step 5) as defined in connection with the chemical pretreatment as defined hereinbefore and hereinafter.
  • the coating material composition used in step 6) is different from each of compositions AAC, ARC, ARC2 and AC.
  • the coating material composition can be, e.g., an electrodeposition coating composition, a primer coating composition, a basecoat composition, or a topcoat including a clearcoat composition. It is, of course, possible to apply more than one composition subsequently to form a multilayer coating system, which is conventionally used, e.g., in the automotive industry.
  • a further subject-matter of the present invention is a substrate, which is a cleaned substrate being obtainable by the cleaning method according to the present invention as defined hereinbefore and hereinafter, a chemically pretreated substrate being obtainable by the chemical pretreatment method according to the present invention as defined hereinbefore and hereinafter, or a coated substrate being obtainable by the coating method according to the present invention as defined hereinbefore and hereinafter.
  • the degree of rinse bath corrosion on the cleaned and conversion coated substrates tested was evaluated visually.
  • the degree of rinse bath corrosion, in particular flash rust in case of steel substrates and white spot formation in case of galvanized steel substrates was determined after either having applied a cleaning composition or after having applied a cleaning composition and a rinsing composition or after having applied a cleaning composition and a rinsing composition and a chemical pretreatment composition.
  • the degree of rinse bath corrosion was classified as follows in three categories:
  • +++ heavy flash rust/white spot formation with coverage of the entire surface of the substrate
  • VDA 233-102 is a cyclic corrosion test with a weekly cycle for determination of the corrosion resistance of the investigated sample. The whole duration of the test was 12 weeks. Undermining (undercreep or creepage) (overall average undermining after 6 and after 12 weeks) has then been determined during perform ing/after having performed the test according to DIN EN ISO 4628-8. Further, stone chip resistance after 12 weeks has been determined as well according to DIN EN ISO 20567-1 , method C.
  • the amounts of certain elements in a sample under analysis is determined using inductively coupled plasma atomic emission spectrometry (ICP-OES) according to DIN EN ISO 11885 (date: September 1 , 2009).
  • ICP-OES inductively coupled plasma atomic emission spectrometry
  • a sample is subjected to thermal excitation in an argon plasma generated by a high- frequency field, and the light emitted due to electron transitions becomes visible as a spectral line of the corresponding wavelength and is analyzed using an optical system. There is a linear relation between the intensity of the light emitted and the concentration of the element in question.
  • the calibration measurements Prior to implementation, using known element standards (reference standards), the calibration measurements are carried out as a function of the particular sample under analysis. These calibrations can be used to determine concentrations of unknown solutions such as the concentration of the amount of titanium and zirconium.
  • a comparative cleaning composition CCC1 has been prepared from a concentrated starting solution.
  • the constituents of said starting solution are displayed in Table 1 .
  • inventive cleaning compositions ICC1 to ICC7 were prepared from the same diluted solution described hereinbefore in item 1.1. However, to the diluted solution one zirconium cations containing water-stable compound/product as indicated below in Table 2 was further added to obtain cleaning compositions ICC1 to ICC7. In addition, several comparative cleaning compositions CCC2 to CCC5 were prepared from the same diluted solution described hereinbefore in item 1.1. However, to the diluted solution one titanium cations containing water-stable compound/product as indicated below in Table 2 was further added to obtain cleaning compositions CCC2 to CCC5. Each of the resulting diluted solutions was then used as process bath.
  • Each bath contained the aforementioned concentrated starting solution in an amount of 20 g/L, to which was added a surfactant and a solubilizer during its preparation.
  • the process bath in each case was operated at a temperature of 55 °C and a pH value of 10.5.
  • Tyzor® 212 and Tyzor® 223 are commercially available zirconium chelate complexes, each being present in form of an alcoholic solution.
  • Tyzor® 131 and Tyzor® TE are commercially available titanates.
  • CRS cold rolled steel
  • HDG hot-dip galvanized steel
  • HDG hot-dip galvanized steel
  • HDG hot-dip galvanized steel
  • EG electrolytically galvanized steel
  • EG electrolytically galvanized steel
  • ZM zinc-aluminum-magnesium alloy coated steel
  • Each of the substrates was treated, i. e. , cleaned, by making use of composition CCC1 or of one of compositions ICC1 to ICC7, or one of compositions CCC2 to CCC5. All compositions were applied using spray application (pressure: 1 bar) for 3 minutes.
  • the substrates were first rinsed with tap water for 30 seconds at 55 °C and subsequently rinsed with deionized water for 30 seconds at 45 °C. Both rinses were applied using dip application.
  • the substrates After having been rinsed the substrates were subjected to a contacting step in order to apply a conversion coating layer onto their cleaned surfaces.
  • a contacting step in order to apply a conversion coating layer onto their cleaned surfaces.
  • the substrates were contacted with a commercially available acidic aqueous chemical pretreatment composition (Oxsilan® 9835), which inter alia comprises zirconium cations, fluoride anions and an organosilane.
  • the contacting step was performed in each case for 180 seconds by dipping the substrates into the acidic aqueous composition.
  • the temperature of the acidic aqueous composition was 30 °C before immersion.
  • Electrodeposition coating material (Cathoguard® 800) was applied on the conversion coated surface of the substrate and cured at 175 °C for 25 minutes.
  • Table 3 demonstrate the improving effect of zirconium cations present in the cleaning composition on the rinse bath corrosion such as the formation of flash rust on steel substrates such as CRS and the formation of white spots on different zinc-coated substrates, respectively.
  • CCC1 the reference system
  • Zirconium could not be detected on the surface of the substrates when using X-ray fluorescence spectroscopy (XRF), presumably due to the low concentrations employed in this study.

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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)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne un procédé de nettoyage d'une surface métallique d'un substrat comprenant au moins l'étape 1) de mise en contact de la surface avec une composition alcaline aqueuse AAC pour nettoyer le substrat, qui comprend de l'eau, une source d'induction d'alcalinité, éventuellement un agent complexant, un tensioactif, et éventuellement des anions borate et/ou éventuellement des anions phosphate condensés, et éventuellement également l'étape 2) de rinçage de la surface nettoyée obtenue après l'étape 1) au moins une fois avec une composition de rinçage aqueuse ARC, des cations Zr étant présents dans la composition AAC lorsque l'étape facultative 2) n'est pas effectuée ou étant présents dans au moins l'une des compositions AAC et ARC lorsque l'étape facultative 2) est effectuée, la composition alcaline aqueuse AAC en tant que telle et un concentré utilisable pour sa préparation, un procédé de prétraitement chimique de ladite surface de substrat nettoyée susmentionnée, un procédé de revêtement de ladite surface de substrat chimiquement prétraitée, et un substrat possédant une surface nettoyée, chimiquement prétraitée ou revêtue pouvant être obtenue par l'un des procédés susmentionnés.
EP24718092.0A 2023-04-04 2024-04-03 Composition de nettoyage et procédé de nettoyage de surfaces métalliques pour empêcher la corrosion d'un bain de rinçage Pending EP4689227A2 (fr)

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PCT/EP2024/058995 WO2024208859A2 (fr) 2023-04-04 2024-04-03 Composition de nettoyage et procédé de nettoyage de surfaces métalliques pour empêcher la corrosion d'un bain de rinçage

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KR20250168577A (ko) 2025-12-02
CN120882904A (zh) 2025-10-31
WO2024208859A3 (fr) 2024-11-14
WO2024208859A2 (fr) 2024-10-10

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