EP3303652A1 - Produit de prélavage contenant une amine quaternaire de conditionnement avant un traitement de conversion - Google Patents

Produit de prélavage contenant une amine quaternaire de conditionnement avant un traitement de conversion

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Publication number
EP3303652A1
EP3303652A1 EP16724027.4A EP16724027A EP3303652A1 EP 3303652 A1 EP3303652 A1 EP 3303652A1 EP 16724027 A EP16724027 A EP 16724027A EP 3303652 A1 EP3303652 A1 EP 3303652A1
Authority
EP
European Patent Office
Prior art keywords
methylimidazolium
carbon atoms
composition
less
aqueous composition
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.)
Granted
Application number
EP16724027.4A
Other languages
German (de)
English (en)
Other versions
EP3303652B1 (fr
Inventor
Kevin D. Murnaghan
Michiel Gerard MAAS
Sophie Cornen
Isabel Kinscheck
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3303652A1 publication Critical patent/EP3303652A1/fr
Application granted granted Critical
Publication of EP3303652B1 publication Critical patent/EP3303652B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • 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.
  • 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 metal-oxide-containing agent to reduce the fluoride content in the conversion layer of the actual wet-chemical treatment aqueous sink containing basic compounds immediately following or a drying step is downstream.
  • the reduction of the fluoride content in the conversion layer serves the addition of certain cations selected from calcium, magnesium, zinc, copper or silicon-containing compounds for the conversion of the surface inducing
  • WO 201 1012443 A1 teaches a downstream aqueous sink containing organic compounds having aromatic heterocycles with at least one nitrogen heteroatom ,
  • the object was to further unify the anti-corrosive properties of conversion layers on various metal substrates obtainable by pretreatment with compositions of water-soluble compounds of the elements Zr, Ti and / or Si and in particular to the
  • 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.
  • 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 having only the natural oxide layer
  • This object is achieved by a multi-stage process for corrosion-protective pretreatment of at least partially made of metallic materials
  • composition Materials with an aqueous composition (A) containing a dissolved and / or dispersed salt of a quaternary organic amine ("conditioning"), and subsequently
  • the treated according to the present invention components can be any arbitrarily shaped and designed spatial structures that originate from a fabrication process, in particular also semi-finished products such as strips, sheets, rods, tubes, etc. and
  • a conditioning treatment is carried out with the aqueous composition (A) comprising the dissolved and / or dispersed salt of a quaternary organic amine ("conditioning") an aqueous composition (B) is provided with a sufficient and homogeneous layer coating with respect to the elements Zr, Ti and / or Si, so that a conversion of the metal surfaces of the component is effectively carried out, which provides a potentially good lacquer adhesion base
  • a reproducible layer coating with respect to the elements Zr, Ti and / or Si is achieved, which forms the basis for effective suppression of corrosive infiltration of defects in an additionally applied layer
  • a salt of a quaternary organic amine dissolved or dispersed in water in the aqueous phase has an average particle diameter of less than 1 ⁇ m.
  • the mean particle diameter can according to
  • ISO 13320: 2009 are determined by laser light diffraction from cumulative particle size distributions as so-called D50 value directly in the aqueous composition (A) at 20 ° C.
  • D50 value directly in the aqueous composition (A) at 20 ° C.
  • Composition (A) in step i) increases the suitability of the conversion coating applied in step ii) to be a good paint adhesion base.
  • 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.
  • a quaternary organic amine contained in the aqueous composition (A) is a heterocycle having at least one nitrogen heteroatom of the following structural formula (I):
  • 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-) i ) - (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 each y is a natural number 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 from hydrogen;
  • Y as the ring-constituting divalent radical having not more than 5 bridging atoms, wherein not more than one of carbon atoms
  • Heterobridatom selected from oxygen, nitrogen or sulfur can be bridging atom and the carbon atoms in turn independently of one another with radicals R 1 or such radicals substituted, via which a Anellierung of aromatic homocycles having not more than 6 carbon atoms is realized.
  • the quaternary organic amine is represented by such heterocycles having the backbone of imidazole, imidazoline, pyrimidine, purine and / or quinazoline.
  • the heterocycle according to the structural formula (I) be used as
  • quaternary organic amines which is selected from 1, 2,3-trimethylimidazolium, 1-methyl-3-methylimidazolium,
  • 1-ethoxy-3-methylimidazolium 1-propoxy-3-methylimidazolium, more preferably from 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, however
  • step i) preferably not greater than 5 g / kg, more preferably not greater than 10 g / kg. Above 10 g / kg, 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.
  • Dialkyl phosphonates having preferably not more than 5 carbon atoms preferably from monoalkyl sulfates and / or monoalkyl sulfonates preferably having not more than 5 carbon atoms, more preferably from methyl sulfate, as advantageous for a uniform conversion layer formation in step ii) of the method according to the invention, so that their additional presence accordingly is preferred.
  • the anions (K) are preferably at the same time the anionogenic
  • 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,
  • 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 S0 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.
  • aqueous composition (A) contains a quantity of iron ions which, when in contact with the zinc surfaces, causes a thin coating of iron there, thereby additionally contributing to the standardization of the corrosion protection in the process according to the invention is accessible in particular for surfaces of the material iron.
  • Such icing can, according to the teaching of WO 2008135478 A1, be carried out in an acid medium, preferably in the presence of a reducing agent or in accordance with the teaching of WO 201 1098322 A1 in an alkaline medium, preferably in the presence of
  • the aqueous composition (A) may contain further components according to the invention. In addition to the pH-regulating substances can do this too
  • Composition (A) having 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.
  • Surface-active compounds according to the present invention have an HLB value (hydrophilic-lipophilic balance) of less than 5 or more than 10. The H LB value is calculated using the following formula and can assume values from zero to 20 on the arbitrary scale:
  • Mi molecular weight of the lypophilic group of nonionic surfactant
  • M molecular weight of the nonionic surfactant
  • 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.
  • Conditioner or in a preferred embodiment of the present invention additionally contain quaternary organic amines in competition and thereby counteracts the respective desired technical effect.
  • quaternary organic amines in competition and thereby counteracts the respective desired technical effect.
  • the organic polymer dissolved or dispersed in the context of the invention has a weight-average molar mass M w of at least 5,000 g / mol and in the aqueous phase has an average particle diameter of less than 1 ⁇ m.
  • the mean particle diameter can according to ISO 13320: 2009 means
  • the aqueous composition (A) does not contain any components in an amount that can do so during the conditioning 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.
  • 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 OO 3 and subsequent atomic emission spectroscopy (ICP-OES).
  • XRF X-ray fluorescence analysis
  • ICP-OES atomic emission spectroscopy
  • An inventive method is to prevent the formation of a
  • Conversion layer on the surfaces of the metallic materials of the component preferably characterized in that the aqueous composition (A) in step i) each less than 0.005 g / kg, more preferably in each case less than
  • Composition (A) less than 0.05 g / kg, more preferably less than
  • total fluoride is in a TISAB buffered aliquot of the aqueous
  • composition (A) determined with a fluoride-sensitive electrode at 20 ° C (TISAB: “Total Lonic Strength Adjustment Buffer”), where the volume-related
  • the TISAB buffer is prepared by dissolving 58 g NaCl, 1 g
  • 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 when their solubility in
  • deionized water ( ⁇ ⁇ 1 ⁇ 1 ) is at least 1 g / L at 20 ° C.
  • the total content 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 anti-corrosive properties of the conversion layer, but due to the higher deposition kinetics make it difficult to control the layer support 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 achieving a sufficient conversion of the compounds
  • Particularly preferred representatives are (NH 4 ) 2Zr (OH) 2 (C03) 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, such methods
  • 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 whole particularly preferably no free fluoride is contained.
  • Composition (B) with increasing preference 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 analogously to the procedure for determining the same parameters in the aqueous
  • Composition (A) can be determined. In combination with the conditioning in step i), the best results in terms of corrosion protection are achieved if copper ions are present in the aqueous composition (B) in step ii). In a particularly preferred
  • Composition (B) therefore additionally 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 salts for example copper sulfate, copper nitrate and copper acetate.
  • the content of copper from water-soluble compounds is in the aqueous
  • Composition (B) preferably at least 0.001 g / kg, more preferably at least 0.005 g / kg.
  • the content of copper ions is preferably not above 0.1 g / kg, more preferably not above 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 intervening 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).
  • 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 consists of a previous wet-chemical
  • Treatment step are removed with the adhesive on the component wet film, by means of a water-based liquid medium.
  • the water was based
  • Liquid medium contains no chemical components that have a significant surface coverage of the components made of metallic materials
  • Square meters of the rinsed surfaces preferably at least 1 milligram per square meter of the rinsed surfaces, depleted of these components relative to the particular element or polymeric organic compound, without taking into account gains from 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.
  • 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 there is a significant improvement in the
  • 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.
  • an organic coating especially a powder coating or dip coating, which in turn is preferably an electrodeposition paint.
  • a rinsing step preferably a rinsing step, but more 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.
  • phosphated may 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 described in the published patent applications WO 201 1098322 A1 and WO 2008135478 A1 as a wet-chemical method, which in an equivalent manner immediately before the execution of the
  • Method step i) according to the invention can be used.
  • Zinc and / or galvanized steel it is preferred that the surfaces of the component, which are made of these materials, have an iron occupancy of at least 20 mg / m 2 , but 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 Abstaltung.
  • composition containing a predetermined amount of a "conditioner” in deionized water ( ⁇ ⁇ 1 ⁇ 1 ) without further addition of pH-changing substances;
  • the respective sheet was first rinsed with deionized water ( ⁇ ⁇ ⁇ 1 ) at 20 ° C and then coated with a cathodic dip coating and dried at 180 ° C.
  • Conversion treatment based on a fluoride-free composition in step (D) can not be realized reproducibly a coating layer in the range of 0-20 mg / m 2 of zirconium (No. 1).
  • conditioning on the basis of a pretreatment with an aqueous solution containing polyvinylpyrollidone (No. 2) fails because the conversion layer formation is neither increased nor reproducible overall. Only the addition of imidazolium salts causes a significant conversion of

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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)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

La présente invention concerne un procédé en plusieurs étapes de prétraitement anticorrosion de composants fabriqués à partir de matières métalliques, dans lequel un traitement chimique de conditionnement par voie humide avec une composition aqueuse (A) contenant un sel d'une amine quaternaire est suivi d'un autre traitement chimique par voie humide, à base de composés hydrosolubles des éléments Zr, Ti et/ou Si, au cours duquel se déroule une conversion correspondante des surfaces des matières métalliques qui crée une base de fixation anticorrosion destinée à des revêtements organiques supplémentaires appliqués.
EP16724027.4A 2015-05-29 2016-05-19 Prérinçage contenant une amine quaternaire pour le conditionnement avant un traitement de conversion Active EP3303652B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
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

Publications (2)

Publication Number Publication Date
EP3303652A1 true EP3303652A1 (fr) 2018-04-11
EP3303652B1 EP3303652B1 (fr) 2019-11-20

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US20180066365A1 (en) 2018-03-08
DE102015209910A1 (de) 2016-12-01
CN107683349A (zh) 2018-02-09
EP3303652B1 (fr) 2019-11-20
JP2018517062A (ja) 2018-06-28
KR20180014018A (ko) 2018-02-07
CN107683349B (zh) 2020-05-26
WO2016193005A1 (fr) 2016-12-08
JP6784703B2 (ja) 2020-11-11

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