EP3303652B1 - Prérinçage contenant une amine quaternaire pour le conditionnement avant un traitement de conversion - Google Patents

Prérinçage contenant une amine quaternaire pour le conditionnement avant un traitement de conversion Download PDF

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Publication number
EP3303652B1
EP3303652B1 EP16724027.4A EP16724027A EP3303652B1 EP 3303652 B1 EP3303652 B1 EP 3303652B1 EP 16724027 A EP16724027 A EP 16724027A EP 3303652 B1 EP3303652 B1 EP 3303652B1
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EP
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Prior art keywords
methylimidazolium
particularly preferably
carbon atoms
composition
less
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EP16724027.4A
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German (de)
English (en)
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EP3303652A1 (fr
Inventor
Kevin D. Murnaghan
Michiel Gerard MAAS
Sophie Cornen
Isabel Kinscheck
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C23C22/48—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
    • C23C22/78—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C23F11/143—Salts of amines
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • C23F11/163—Sulfonic acids

Definitions

  • the present invention relates to a multi-stage process for the corrosion-protective pretreatment of components made of metallic materials, wherein on a conditioning wet-chemical treatment with an aqueous composition (A) containing a salt of a quaternary amine, a further wet-chemical treatment based on water-soluble compounds of the elements Zr, Ti and / or Si follows, in the course of which a corresponding conversion of the surfaces of the metallic materials takes place, which provides a corrosion-protecting primer for additionally applied organic coatings.
  • the conversion treatment of metallic surfaces to provide a corrosion-protective coating based on aqueous compositions containing water-soluble compounds of the elements Zr, Ti and / or Si is a technical field extensively described in the patent literature.
  • various variants of such metal pretreatment are known, which either aim at the composition of the conversion-causing agents or resort to further wet-chemical treatment steps in the immediate context of the conversion treatment.
  • the EP 1 455 002 A1 describes, for example, that it is advantageous for conversion treatment by means of previously described compositions which additionally contain fluoride ions as complexing agent and the metal surface-attracting agent, if for reducing the fluoride content in the conversion layer of the actual wet chemical treatment, an aqueous sink containing basic compounds immediately following or a drying step is downstream.
  • the reduction of the fluoride content in the conversion layer serves to add certain cations selected from calcium, magnesium, zinc, copper or silicon-containing compounds to the surface conversion-inducing composition.
  • the US 2010/222248 A1 and EP 2 253 741 A2 each disclose a multi-step process in which the metal surfaces are treated with an aqueous composition containing a salt of a quaternary organic amine selected from heterocycles having at least one quaternary nitrogen heteroatom, followed by a conversion treatment with an aqueous composition containing a titanium or a zirconium Connection.
  • the object was to further standardize the anti-corrosive properties of conversion layers on different metal substrates obtainable by pretreatment with compositions of water-soluble compounds of the elements Zr, Ti and / or Si and in particular to improve the steel surfaces.
  • the average undermigration values in the corrosive delamination after coating layer build-up should be improved.
  • the pretreatment for environmental health reasons should be largely without the presence of fluorides.
  • a pretreatment method according to the present invention must, therefore, in order to realize this aspect, even in the absence of fluorides, a homogeneous and complete conversion of the so-called "free metal surface" so the degreased, purified and only the natural oxide layer having metal surface effect.
  • the components treated according to the present invention can be any arbitrarily shaped and configured spatial structures which originate 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.
  • a conditioning treatment with the aqueous composition (A) comprising the dissolved and / or dispersed salt of a quaternary organic amine is carried out ("conditioning").
  • This conditioning causes that in the course of the wet-chemical treatment with an aqueous composition (B) a sufficient and homogeneous coating layer with respect to the elements Zr, Ti and / or Si is achieved, so that a conversion of the metal surfaces of the component is effectively carried out, the one potentially good Lackhaft ground provides.
  • a reproducible layer support with respect to the elements Zr, Ti and / or Si which is the basis for effective suppression of corrosive infiltration of defects in an additionally applied lacquer coating.
  • a salt of a quaternary organic amine dissolved or dispersed in water in the meaning of the invention takes up an average particle diameter of less than 1 ⁇ m in the aqueous phase.
  • the average particle diameter can be determined according to ISO 13320: 2009 by means of laser light diffraction from cumulative particle size distributions as a so-called D50 value directly in the aqueous composition (A) at 20 ° C.
  • a quaternary organic amine in the context of the present invention contains at least one nitrogen atom which has exclusively covalent bonds with carbon atoms and therefore possesses a permanent positive charge.
  • the quaternary organic amines have a weight average molecular weight M w of less than 5,000 g / mol.
  • the aqueous composition (A) contains a salt of a quaternary organic amine selected from heterocycles having at least one quaternary nitrogen heteroatom and the following structural formula (I): with the radicals R 1 , R 2 and R 3 , which are each selected from hydrogen, branched or unbranched aliphatics having not more than 6 carbon atoms or the radical - (CR 4 R 4 ) x - [Z (R 4 ) (p-) 1) - (CR 4 R 4 ) y ] n -Z (R 4 ) p , where Z is each selected from oxygen or nitrogen and p in the case where Z is nitrogen, takes the value 2 and otherwise equals 1, and x and y are each natural numbers from 1 to 4 and n is also a natural number from 0 to 4 and R 4 is selected from hydrogen or branched or unbranched aliphatics having not more than 6 carbon atoms, with with the proviso that at least one of R 2 or R 3 is not selected
  • the quaternary organic amine is represented by such heterocycles having the backbone of imidazole, imidazoline, pyrimidine, purine and / or quinazoline.
  • quaternary organic amines which is selected from 1,2,3-trimethylimidazolium, 1-methyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium, 1-isopropyl-3-methylimidazolium, 1-propyl 3-methylimidazolium, 1- (n-butyl) -3-methylimidazolium, 1- (isobutyl) -3-methylimidazolium, 1-methoxy-3-methylimidazolium, 1-ethoxy-3-methylimidazolium, 1-propoxy-3-methylimidazolium , more preferably 1,2,3-trimethylimidazolium.
  • the proportion of the quaternary organic amine in the aqueous composition (A) is at least 0.05 g / kg, preferably at least 0.2 g / kg, more preferably at least 0.4 g / kg, but preferably is not greater than 5 g / kg, more preferably not greater than 10 g / kg.
  • step i) even if the conditioning in step i) is followed by a rinsing step, no further suppression of corrosive delamination after paint build-up is observed, so that any amount of quaternary organic amine beyond this would be uneconomically used in the process according to the invention.
  • All counterions to the quaternary organic amine are generally all anions, in particular sulfates, nitrates, chlorides, carbonates and organic anions such as alkyl sulfates, alkyl sulfonates, alkyl phosphates and / or alkyl phosphonates.
  • anions (K) has been selected from monoalkyl sulfates, monoalkyl sulfonates, dialkyl phosphates and / or dialkyl phosphonates preferably having not more than 5 carbon atoms, preferably monoalkyl sulfates and / or monoalkyl sulfonates preferably not more than 5 carbon atoms, most preferably methyl sulfate advantageous for a uniform conversion layer formation in step ii) of the method according to the invention, so that their additional presence is correspondingly preferred.
  • the anions (K) are preferably at the same time the anionic constituent of the salt of the quaternary organic amine, so that the corresponding salt therewith is both source of the quaternary amine and source of the anion (K) and the ionic load in the aqueous composition (A ) can thus be reduced to a minimum.
  • Suitable sources of the anions (K) are therefore in addition to the salts of the alkali and / or alkaline earth metals and the corresponding ammonium salts, in particular the corresponding salts of the previously described quaternary organic amines.
  • the proportion of anions (K) in the aqueous composition (A) is preferably at least 0.05 g / kg, more preferably at least 0.2 g / kg, particularly preferably at least 0.4 g / kg, but the proportion is preferably not greater than 5 g / kg, more preferably not greater than 3 g / kg, each calculated as the equivalent amount of SO 4 based on the aqueous composition (A). Above 5 g / kg, even if the conditioning in step i) is followed by a rinsing step, no further increase or equalization of the conversion layer formation in step ii) causes, so that any amount beyond the conditioner would be used uneconomically in the process according to the invention.
  • the pH of the aqueous composition (A) in step i) can be chosen freely as far as possible and is usually in the range from 2 to 14, preferably above 3.0, more preferably above 4.0, particularly preferably above 5, 0, but preferably below 12.0, more preferably below 10.0, and most preferably below 8.0.
  • the aqueous composition (A) additionally contains an amount of iron ions, which in contact with the zinc surfaces there a thin coating layer causes iron and thus additionally contributes to the standardization of corrosion protection, which is accessible in the process according to the invention in particular for surfaces of the material iron.
  • Such an icing can, according to the doctrine of WO 2008135478 A1 in an acidic medium, preferably in the presence of a reducing agent or according to the teaching of WO 2011098322 A1 in the alkaline medium, preferably in the presence of complexing agents and phosphate ions.
  • the aqueous composition (A) may contain further components according to the invention.
  • these may also be surface-active compounds whose use in an aqueous composition (A) with a cleaning action is preferred.
  • the aqueous composition (A) contains less than 0.05 g / kg, preferably less than 0.01 g / kg, more preferably less than 0.001 g / kg of surface active compounds not composed of quaternary organic amines are so that the interaction of the surface-active compounds with the surfaces of the metallic materials of the component does not compete with that of the quaternary organic amine and thereby counteracts the respective desired technical effect.
  • HLB hydrophilic-lipophilic balance
  • the aqueous composition (A) in step i) of the process according to the invention is less than 0.5 g / kg, more preferably less than 0.1 g / kg, particularly preferably less than 0.05 g / kg of dissolved and / or dispersed organic polymers which are not quaternary organic amines. This ensures, as before, the presence of surface-active compounds that the interaction of such polymers with the surfaces of the metallic materials of the component does not compete with that of the conditioner or quaternary organic amines additionally present in a preferred embodiment of the present invention and thereby each desired technical effect is counteracted.
  • An organic polymer dissolved or dispersed in this connection of the invention has a weight average molecular weight M w of at least 5000 g / mol and in the aqueous phase has an average particle diameter of less than 1 ⁇ m.
  • the average particle diameter can be determined according to ISO 13320: 2009 by means of laser light diffraction from cumulative particle size distributions as a so-called D50 value directly in an aqueous composition (A) at 20 ° C.
  • the aqueous composition (A) does not contain any components in such an amount that it is capable of forming a conversion layer on a surface of a metallic material of the component during the period of time provided for the conditioning in step i).
  • a conversion layer in the course of the conditioning in step i) of the method according to the invention is present when a cover layer is produced wet-chemically on the respective surface of the metallic material, the phosphates, oxides and / or hydroxides of elements of the titanium group, vanadium group and / or chromium group or phosphates of the elements calcium, iron and / or zinc in one Coating layer of at least 5 mg / m 2 based on the respective sub-group element or of at least 50 mg / m 2 drawn on the element phosphorus.
  • the corresponding subgroup elements can be determined quantitatively by X-ray fluorescence analysis (XRF), while the layer coverage with respect to the element phosphorus can be determined quantitatively by pickling the surfaces of the metallic materials in aqueous 5% by weight CrO 3 and subsequent atomic emission spectroscopy (ICP-OES).
  • XRF X-ray fluorescence analysis
  • ICP-OES atomic emission spectroscopy
  • a method according to the invention is preferably characterized in that the aqueous composition (A) in step i) is less than 0.005 g / kg, particularly preferably less than 0.001 g / kg to water-soluble compounds of the elements Zr, Ti and / or Si based on the respective element, preferably less than 1 g / kg of water-soluble compounds of the elements Zn, Mn and Ca based on the respective element and / or preferably less than 0.05 g / kg, more preferably less than 0.01 g / kg of free fluoride determined with a fluoride-sensitive electrode at 20 ° C contains.
  • the total content of fluorides in the aqueous composition (A) is less than 0.05 g / kg, more preferably less than 0.02 g / kg, particularly preferably less than 0.01 g / kg.
  • the total fluoride content (total fluoride) is determined in a TISAB-buffered aliquot of the aqueous composition (A) with a fluoride-sensitive electrode at 20 ° C (TISAB: "Total Lonic Strength Adjustment Buffer"), wherein the volume-related mixing ratio of buffer to aliquots of the aqueous composition (A) 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 to pH 5.3 by 5N NaOH and making up to total volume of 1000 ml again with deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ).
  • an amount of active components sufficient to form a conversion layer should be present in the acidic aqueous composition (B).
  • the aqueous composition (B) in step ii) preferably at least 0.01 g / kg, more preferably at least 0.05 g / kg, particularly preferably at least 0.1 g / kg of water-soluble compounds of the elements Zr , Ti or Si based on the respective element Zr, Ti or Si.
  • such compounds according to the present invention are considered to be water-soluble if their solubility in deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ) is at least 1 g / L at 20 ° C.
  • the total proportion of these compounds, based on the elements Zr, Ti and Si, is preferably not greater than 0.5 g / kg, since higher contents usually do not further improve the corrosion-protecting properties of the conversion layer, but due to the higher deposition kinetics complicate the control of the coating layer with respect to these elements.
  • fluorine-free water-soluble compounds of the elements Zr, Ti or Si in the aqueous composition (B) are also suitable for producing a sufficient conversion of the surfaces of the metallic materials of the component and are therefore preferred.
  • Particularly preferred representatives are (NH 4 ) 2 Zr (OH) 2 (CO 3 ) 2 , ZrO (NO 3 ) 2 or TiO (SO 4 ) or silanes having at least one covalent Si-C bond.
  • step ii) for effecting the conversion of the surfaces of the metallic materials of the components can be dispensed with in the present inventive method due to the conditioning in step i). Accordingly, those methods are preferred according to the invention in which the proportion of free fluoride in the aqueous composition (B) with increasing preference is less than 0.05 g / kg, 0.01 g / kg, 0.001 g / kg and 0.0001 g / kg and most preferably no free fluoride is contained.
  • the total proportion of fluorides (total fluoride) in the aqueous composition (B) with increasing preference is less than 0.05 g / kg, 0.02 g / kg, 0.01 g / kg, 0.001 g / kg and 0.0001 g / kg and most preferably no fluoride is included.
  • the proportion of free fluoride and the total content of fluorides can be determined analogously to the procedure for determining the same parameters in the aqueous composition (A).
  • the aqueous composition (B) additionally contains water-soluble compounds which are a source of copper ions, preferably in the form of water-soluble salts, for example copper sulfate, copper nitrate and copper acetate.
  • water-soluble compounds which are a source of copper ions, preferably in the form of water-soluble salts, for example copper sulfate, copper nitrate and copper acetate.
  • such compounds according to the present invention are considered to be water-soluble if their solubility in deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ) is at least 1 g / L at 20 ° C.
  • the content of copper of water-soluble compounds in the aqueous composition (B) 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 pH of the aqueous composition (B) is preferably in the acidic range, more preferably in the range of 2.0 to 5.0, particularly preferably in the range of 2.5 to 3.5.
  • the aqueous composition (B) contains nitrate ions as an accelerator of the conversion layer formation, wherein the proportion of nitrate ions is preferably at least 0.5 g / kg, but for reasons of economy preferably does not exceed 4 g / kg.
  • the success of the invention occurs largely independently of the performance of one of the conditioning in step i) immediately following rinsing and / or drying step. Differences in the performance of the process caused by an intermediate rinsing step can be regularly absorbed by a moderate increase in the concentration of quaternary organic amine and the anions (K) contained in the aqueous composition (A).
  • the general suitability of the method to solve the problem underlying the invention in any case remains unaffected by the performance of a rinsing and / or drying step between steps i) and ii).
  • step i) in a process according to the invention it is preferable for step i) in a process according to the invention to be followed directly by a rinsing step to separate the active components in the individual treatment steps, wherein preferably no drying step takes place before step ii).
  • a rinsing step according to the invention is always the removal of water-soluble residues, not firmly adhering chemical compounds and loose solid particles from the component to be treated, which are removed from a previous wet-chemical treatment step with the adhesive on the component wet film, by means of a water-based liquid medium.
  • the water-based liquid medium contains no chemical components that cause a significant surface coverage of the components made of metallic materials with subgroup elements, semi-metal elements or polymeric organic compounds.
  • such a significant surface coverage is present when the liquid medium of the sink is depleted by at least 10 milligrams per square meter of the flushed surfaces, preferably by at least 1 milligram per square meter of the flushed surfaces, based on these components relative to the respective element or the respective polymeric organic compound without taking account of gains due to carryover and losses due to removal of wet films adhering to the component.
  • a drying step is any method step in which the provision and use of technical means is intended to dry the aqueous liquid film adhering to the surface of the component, in particular by supplying thermal energy or impressing an air flow.
  • the components that are treated in the method according to the invention at least partially made of metallic materials.
  • Preferred metallic materials for which an improvement in the properties of the conversion layer as a lacquer adhesion base is clearly evident are iron and alloys of iron, in particular steel.
  • alloys of iron are materials which are formed by at least 50 at.% Of the respective material of iron atoms. On surfaces of iron and its alloys, a significant improvement in corrosion protection occurs in the corrosive infiltration of paint defects that even largely independent of whether immediately after the conditioning in step i) followed by a rinsing and / or drying step.
  • step ii) is preferably followed by the application of an organic coating, especially a powder coating or dip coating, which in turn is preferably an electrodeposition paint.
  • the electrodeposition coating preferably follows a rinsing step, but particularly preferably no drying step.
  • the component at least partially surfaces of the materials iron and / or steel, preferably at least 50%, more preferably at least 80% of the surface of the component, the surfaces of metallic materials, from surfaces of the materials iron and / or steel are formed.
  • composite structures and in particular components which, in addition to surfaces of the materials iron and / or steel, also have surfaces of the materials zinc and / or galvanized steel and aluminum, which may optionally be additionally phosphated, can be treated in the process according to the invention.
  • the component has surfaces of the materials zinc and / or galvanized steel
  • same surfaces be treated with a thin amorphous layer containing iron, so that the surfaces of these materials have an equally effective conditioning in step i ) of the method according to the invention, as is commonly found for the surfaces of the materials iron and / or steel.
  • a particularly effective icing of the surfaces of zinc and / or galvanized steel is disclosed in the published patent applications WO 2011098322 A1 and WO 2008135478 A1 each described as a wet-chemical process, which can be applied in an equivalent manner immediately before carrying out the process step i) according to the invention.
  • the component comprises at least partially of the materials zinc and / or galvanized steel, that the surfaces of the component, which are made of these materials, an iron occupancy of at least 20 mg / m 2 , however preferably not more than 150 mg / m 2 .
  • steel sheets are subjected to a multi-stage process for corrosion-protective pretreatment.
  • the suitability of such pretreated and provided with a paint layer metal sheets to represent a good Lackhaftground is tested in a test according to DIN EN ISO 4628-8 for corrosive delamination.
  • the respective sheet was first rinsed with deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ) at 20 ° C. and then coated with a cathodic dip coating and dried at 180 ° C. (dry layer thickness: 18-20 ⁇ m, CathoGuard ® 800 from BASF Coatings).
  • Table 1 below shows the various organic compounds used in the conditioning in step (C).
  • composition C1 in Table 1 is not according to the invention.
  • Tab. 1 Used compositions in conditioning conditioner Quantity in g / kg anion cation PH value C1 2 * - - 4.3 C2 2.5 chloride 1-ethyl-3-methylimidazolium 5.5 C3 2.5 methyl sulfate 1,2,3-trimethylimidazolium 7.5 * Polyvinyl pyrollidone (Mw ⁇ 160,000 g / mol)

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
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Claims (13)

  1. Procédé en plusieurs étapes pour le prétraitement anticorrosion de composants constitués au moins partiellement de matériaux métalliques, dans lequel
    i) au moins une partie des surfaces du composant formé par les matériaux métalliques est mise en contact avec une composition aqueuse (A) comprenant un sel dissous et/ou dispersé d'une amine organique quaternaire choisie parmi les hétérocycles ayant au moins un hétéroatome d'azote quaternaire et ayant la formule de structure (I) suivante :
    Figure imgb0005
     avec les radicaux R1, R2 et R3, qui sont respectivement choisis parmi l'hydrogène, les aliphates ramifiés ou non ramifiés ayant au maximum 6 atomes de carbone ou le radical -(CR4R4)x-[Z(R4)(p-1)-(CR4R4)y]n-Z(R4)p, où Z est respectivement choisi parmi l'oxygène ou l'azote et p est égal à 2 dans le cas où Z est l'azote et est par ailleurs égal à 1 et x et y sont chacun des nombres naturels de 1 à 4 et n est également un nombre naturel de 0 à 4 et R4 est choisi parmi l'hydrogène ou des aliphates ramifiés ou non ramifiés ayant au maximum 6 atomes de carbone, à la condition qu'au moins un des radicaux R2 ou R3 n'est pas choisi parmi l'hydrogène ;
    dans laquelle Y est un radical divalent constituant le noyau, n'ayant pas plus de 5 atomes de pont, dans lequel pas plus d'un hétéroatome de pont autre que des atomes de carbone, sélectionné parmi l'oxygène, l'azote ou le soufre, peut être un atome de pont, et les atomes de carbone se présentent à leur tour substitués par des radicaux R1 ou de tels radicaux indépendamment les uns des autres, par lesquels est réalisée la réaction d'annélation des homocycles aromatiques ayant au plus 6 atomes de carbone,
    puis
    ii) au moins la même partie des surfaces du composant formé par les matériaux métalliques est mise en contact avec une composition aqueuse (B) contenant un ou plusieurs composés hydrosolubles des éléments Zr, Ti et/ou Si.
  2. Procédé selon la revendication 1, caractérisé en ce que le radical Y divalent constituant le noyau est choisi parmi l'éthylène, l'éthènediyle, le 1,3- propanediyle, le 1,3-propènediyle, le 1,4-butanediyle, le 1,4-butènediyle, le 1,4-butylènediyle et le 1,4-butadiène-diyle, - CH=N-, -CH2-NH-, la (N,N-diméthylène)amine et la (N-méthylène-N-méthylylidène)amine, de manière préférée parmi l'éthènediyle, le 1,4-butadiène-diyle, -C=N- ou la (N-méthylène-N-méthylylidène)amine, de manière particulièrement préférée parmi l'éthènediyle ou -C=N- et de manière spécialement préférée parmi l'éthènediyle, dans lequel l'hydrogène lié par covalence à des atomes de carbone peut être substitué par les membres classiques d'un radical R1.
  3. Procédé selon l'une ou les deux des revendications précédentes, caractérisé en ce que l'amine organique quaternaire est choisie parmi le 1,2,3-triméthylimidazolium, le 1-méthyl-3-méthylimidazolium, le 1-éthyl-3-méthylimidazolium, le 1-isopropyl-3-méthylimidazolium, 1-propyl-3-méthylimidazolium, 1-(n-butyl)-3-méthylimidazolium, le 1-(isobutyl)-3-méthylimidazolium, 1-méthoxy-3-méthylimidazolium, 1-éthoxy-3-méthylimidazolium, le 1-propoxy-3-méthylimidazolium, de préférence de 1,2,3-triméthylimidazolium.
  4. Procédé selon une ou plusieurs des revendications ci-dessus, caractérisé en ce que la composition (A) de l'étape i) contient en outre des anions (K) choisis parmi les sulfates monoalkyliques, les sulfonates monoalkyliques, les phosphates dialkyliques et/ou les phosphonates dialkyliques ne comportant de préférence pas plus de 5 atomes de carbone, de préférence des sulfates monoalkyliques et/ou des sulfonates monoalkyliques ne comportant de préférence pas plus de 5 atomes de carbone, de manière particulièrement préférée du sulfate méthyle.
  5. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la teneur en amine organique quaternaire de la composition (A) est d'au moins 0,05 g/kg, de préférence d'au moins 0,2 g/kg, de manière particulièrement préférée d'au moins 0,4 g/kg, néanmoins de préférence d'au maximum 20 g/kg, de manière particulièrement préférée d'au maximum 10 g/kg.
  6. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce qu'aucune couche de conversion n'est produite sur les surfaces des composants métalliques à l'étape i).
  7. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la composition (A) contient moins de 0,05 g/kg, de préférence moins de 0,01 g/kg, de manière particulièrement préférée moins de 0,001 g/kg de composés tensioactifs non constitués d'amines organiques quaternaires.
  8. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la composition (B) de l'étape ii) contient au moins 0,01 g/kg, de préférence au moins 0,05 g/kg, de manière particulièrement préférée au moins 0,1 g/kg de composés hydrosolubles des éléments Zr, Ti ou Si, par rapport à chaque élément.
  9. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la composition (B) de l'étape ii) contient moins de 0,05 g/kg, de préférence moins de 0,01 g/kg, de manière particulièrement préférée moins de 0,001 g/kg de fluorure libre.
  10. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la teneur totale en fluorure dans la composition (B) à l'étape ii) est inférieure à 0,05 g/kg, de préférence inférieure à 0,01 g/kg, de manière particulièrement préférée inférieure à 0,001 g/kg et de manière spécialement préférée inférieure à 0,0001 g/kg.
  11. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que, avant l'étape i), les composants sont nettoyés et dégraissés, de préférence en les mettant en contact avec des compositions aqueuses contenant des composés tensioactifs.
  12. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce qu'entre les étapes de procédé i) et ii) l'on effectue une étape de rinçage et de préférence l'on n'effectue pas d'étape de séchage.
  13. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que le composant présente au moins partiellement des surfaces des matériaux fer et/ou acier et de préférence au moins 50 %, de manière particulièrement préférée au moins 80 %, de la surface des matériaux métalliques du composant est formée de surfaces des matériaux fer et/ou acier.
EP16724027.4A 2015-05-29 2016-05-19 Prérinçage contenant une amine quaternaire pour le conditionnement avant un traitement de conversion Active EP3303652B1 (fr)

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DE102015209910.5A DE102015209910A1 (de) 2015-05-29 2015-05-29 Vorspüle enthaltend ein quartäres Amin zur Konditionierung vor einer Konversionsbehandlung
PCT/EP2016/061209 WO2016193005A1 (fr) 2015-05-29 2016-05-19 Produit de prélavage contenant une amine quaternaire de conditionnement avant un traitement de conversion

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Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3365313A (en) * 1962-06-11 1968-01-23 American Cyanamid Co Anti-corrosion compositions
IT1207517B (it) * 1985-12-19 1989-05-25 Enichem Sintesi Inibitori di corrosione sottosforzo di acciai inossidabili.
DE4441710A1 (de) * 1994-11-23 1996-05-30 Henkel Kgaa Korrosionsschutz und Reibungsverminderung von Metalloberflächen
DE19649285A1 (de) * 1996-11-28 1998-06-04 Henkel Kgaa Verfahren zum Schutz von Metalloberflächen gegenüber Korrosion in flüssigen oder gasförmigen Medien
JP4526807B2 (ja) 2002-12-24 2010-08-18 日本ペイント株式会社 塗装前処理方法
US20050012077A1 (en) * 2003-05-28 2005-01-20 Lonza Inc. Quaternary ammonium carbonates and bicarbonates as anticorrosive agents
US20050003978A1 (en) * 2003-05-28 2005-01-06 Lonza Inc. Quaternary ammonium carbonates and bicarbonates as anticorrosive agents
DE10358310A1 (de) * 2003-12-11 2005-07-21 Henkel Kgaa Zweistufige Konversionsbehandlung
MY148568A (en) * 2004-12-09 2013-04-30 Lonza Ag Quaternary ammonium salts as a conversion coating or coating enhancement
DE102006018216B4 (de) * 2006-04-18 2008-09-25 Chemetall Gmbh Verfahren zum demulgierenden Reinigen von metallischen Oberflächen
FR2909667B1 (fr) * 2006-12-12 2009-02-20 Inst Francais Du Petrole Elimination de l'acetonitrile dans la charge olefinique des procedes de production d'ethers par mise en oeuvre de liquides ioniques.
DE102007021364A1 (de) 2007-05-04 2008-11-06 Henkel Ag & Co. Kgaa Metallisierende Vorbehandlung von Zinkoberflächen
DE102007000501A1 (de) * 2007-10-15 2009-04-16 Chemetall Gmbh Reinigerzusammensetzung für metallische Oberflächen
DE102009028025A1 (de) 2009-07-27 2011-02-03 Henkel Ag & Co. Kgaa Mehrstufiges Verfahren zur Behandlung von Metalloberflächen vor einer Tauchlackierung
DE102009029334A1 (de) * 2009-09-10 2011-03-24 Henkel Ag & Co. Kgaa Zweistufiges Verfahren zur korrosionsschützenden Behandlung von Metalloberflächen
DE102010001686A1 (de) 2010-02-09 2011-08-11 Henkel AG & Co. KGaA, 40589 Zusammensetzung für die alkalische Passivierung von Zinkoberflächen
WO2012045712A1 (fr) * 2010-10-05 2012-04-12 Basf Se Procédé pour passiver une surface métallique
WO2012045725A1 (fr) * 2010-10-05 2012-04-12 Basf Se Procédé pour passiver une surface métallique au moyen d'une composition basique
BR112014003156A2 (pt) * 2011-08-10 2017-03-14 Basf Se método para a passivação de uma superfície metálica, e, camada de passivação sobre uma superfície metálica

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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CN107683349B (zh) 2020-05-26
US20180066365A1 (en) 2018-03-08
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EP3303652A1 (fr) 2018-04-11
CN107683349A (zh) 2018-02-09
JP6784703B2 (ja) 2020-11-11
JP2018517062A (ja) 2018-06-28
KR20180014018A (ko) 2018-02-07

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