WO2021104976A1 - Procédé d'économie de ressources pour activer une surface métallique avant un processus de phosphatation - Google Patents

Procédé d'économie de ressources pour activer une surface métallique avant un processus de phosphatation Download PDF

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Publication number
WO2021104976A1
WO2021104976A1 PCT/EP2020/082618 EP2020082618W WO2021104976A1 WO 2021104976 A1 WO2021104976 A1 WO 2021104976A1 EP 2020082618 W EP2020082618 W EP 2020082618W WO 2021104976 A1 WO2021104976 A1 WO 2021104976A1
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Prior art keywords
particularly preferably
colloidal
aqueous solution
acid
mmol
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PCT/EP2020/082618
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German (de)
English (en)
Inventor
Ralf POSNER
Christina ANGENENDT
Jan-Willem Brouwer
Frank-Oliver Pilarek
Ulrike Schmidt-Freytag
Kristof WAPNER
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Henkel Ag & Co. Kgaa
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Priority to JP2022531060A priority Critical patent/JP2023505069A/ja
Priority to CN202080081532.6A priority patent/CN114729457B/zh
Priority to EP20807405.4A priority patent/EP4065749B1/fr
Priority to MX2022006302A priority patent/MX2022006302A/es
Priority to KR1020227017348A priority patent/KR20220106125A/ko
Publication of WO2021104976A1 publication Critical patent/WO2021104976A1/fr
Priority to US17/664,665 priority patent/US20220282381A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—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 containing also phosphates
    • C23C22/362—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 containing also phosphates containing also zinc cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated

Definitions

  • the present invention relates to a method for the layer-forming phosphating of metallic surfaces using a colloidal, aqueous solution as the activation stage containing a dispersed particulate component, the particulate component containing, in addition to dispersed inorganic compounds of phosphates of polyvalent metal cations, polymeric organic compounds as dispersing aids, at least in part are composed of styrene and / or an ⁇ -olefin with no more than 5 carbon atoms and are partly composed of maleic acid, its anhydride and / or its imide, the polymeric organic compounds additionally having polyoxyalkylene units.
  • the cleaning and rinsing stages preceding the activation stage as well as the activation stage itself can be operated in a resource-saving manner without loss of activation performance using process water, the colloidal, aqueous solution containing at least 0.5 mmol / L of alkaline earth metal ions dissolved in water.
  • the layer-forming phosphating is a method that has been practiced for decades and has been intensively investigated for applying crystalline, corrosion-protective coatings to metallic surfaces, in particular to materials made of the metals iron, zinc and aluminum.
  • the zinc phosphating which is particularly well established for corrosion protection, takes place in a layer thickness of a few micrometers and is based on a corrosive pickling of the metallic material in an acidic aqueous composition containing zinc ions and phosphates. In the course of the pickling process, an alkaline diffusion layer develops on the metal surface, which extends into the interior of the solution and within which poorly soluble crystallites form, which precipitate directly at the interface with the metallic material and continue to grow there.
  • Suitable dispersions are colloidal, mostly neutral to alkaline, aqueous compositions based on phosphate crystallites which, in their crystal structure, have only slight crystallographic deviations from the type of zinc phosphate layer to be deposited.
  • WO 98/39498 A1 teaches in particular bivalent and trivalent phosphates of the metals Zn, Fe, Mn, Ni, Co, Ca and Al, where technically preferred phosphates of the metal zinc are used for activation for a subsequent zinc phosphating.
  • An activation stage based on dispersions of bivalent and trivalent phosphates requires a high level of process control in order to keep the activation performance constantly at an optimal level, especially when treating a series of metallic components.
  • aqueous solution must lead to a deterioration in the activation performance. A deterioration is initially noticeable in increasing layer weights in the subsequent phosphating and finally leads to the formation of defective or inhomogeneous phosphate layers.
  • Additivation has always been necessary up to now and when activating with particulate phosphates usually includes the addition of condensed phosphates for colloid stabilization and, additionally or alternatively, the use of other complexing agents to mask water hardness or polyvalent metal ions introduced from previous cleaning and rinsing stages to counteract an accelerated formation of colloid agglomerates and thus the sedimentation of the colloidally dispersed bath species.
  • the dosage of condensed phosphates and / or complexing agents requires precise analytical monitoring, as there is both a process-critical minimum amount that must be adhered to and a system-specific upper limit, below or above which the activation performance is negatively influenced.
  • This relates first of all to the ability of the colloidal, aqueous solution to activate the metal surfaces to be phosphated as uniformly and comprehensively as possible with comparatively little use of material and thus to create homogeneous, finely crystalline coatings in the phosphating stage, so that with excellent paint adhesion properties, there is also a high electrical penetration resistance and in this way a correspondingly good wraparound of the paint is realized in the subsequent electrodeposition coating. Furthermore, for the aspect of the improved robustness of such a method, it is necessary that a higher tolerance to introduced and enriched foreign ions and a high stability with regard to the structural and chemical nature of the colloidal constituent is guaranteed. All of this with the aim of establishing a pretreatment line for phosphating, in particular for zinc phosphating, which can be operated in continuous operation, conserving resources and with little process engineering effort.
  • This complex task profile is surprisingly achieved through the use of a specific polymeric dispersing aid to stabilize the colloidal component of an activation stage based on particulate phosphates. Due to the extremely efficient stabilization of the particulate component causing the activation, the special dispersing aid ensures that even comparatively low proportions of colloids are able to bring about homogeneous, closed phosphate coatings without a significant decrease in the activation performance after the steady state of a pretreatment line has been maintained is detectable. The use of the specific dispersing aid therefore makes it possible to dispense entirely with additives with condensed phosphates and thus to significantly reduce the process engineering effort when carrying out a process for phosphating in continuous operation.
  • the present invention therefore relates to a method for the anti-corrosion pretreatment of a metallic material selected from zinc, iron or aluminum or a component which is at least partially composed of such metallic materials in which the metallic material or the component is in successive process steps are first activated (i) and then phosphated (ii), in particular zinc phosphated, the activation in process step (i) by bringing the metallic material or the component into contact with a colloidal, aqueous solution in the dispersed particulate component (a) of the solution
  • (a1) at least one particulate inorganic compound which is composed of phosphates of polyvalent metal cations at least partially selected from hopeite, phosphophyllite, scholzite and / or hureaulite, and
  • (A2) at least one polymeric organic compound which is at least partly composed of styrene and / or an ⁇ -olefin having not more than 5 carbon atoms and at least partly composed of maleic acid, its anhydride and / or its imide, the polymeric organic compound additionally has polyoxyalkylene units, the colloidal, aqueous solution containing at least 0.5 mmol / L of alkaline earth metal ions dissolved in water.
  • the dispersed particulate component (a) of the colloidal, aqueous solution in the activation (i) of the process according to the invention is that solid fraction which, after drying the retentate of an ultrafiltration, of a defined partial volume of the aqueous dispersion with a nominal exclusion limit of 10 kD (NMWC, Nominal Molecular Weight Cut Off) remains.
  • the ultrafiltration is carried out with the addition of deionized water (K ⁇ IpScnr 1 ) until a conductivity below 10 pScnr 1 is measured in the filtrate.
  • an organic compound is polymeric if its weight-average molar mass is greater than 500 g / mol.
  • the molar mass is determined via the molar mass distribution curve of a sample of the respective reference size, which was determined experimentally by size exclusion chromatography with a concentration-dependent refractive index detector at 30 ° C. and calibrated against polyethylene glycol standards.
  • the evaluation of the molar mass mean values is carried out with the aid of a computer using the strip method with a calibration curve of the 3rd order.
  • a suitable column material is hydroxylated polymethacrylate and an aqueous solution of 0.2 mol / L sodium chloride as an eluent,
  • the colloidal, aqueous solution contains at least 1.0 mmol / L, particularly preferably at least 1.5 mmol / L, of alkaline earth metal ions dissolved in water during activation.
  • This advantage over conventional activation baths is particularly important when phosphating components in series, i.e. during ongoing operation of a pretreatment line for phosphating.
  • a large number of specific components which at least partially consist of zinc, iron or aluminum, are treated in series.
  • a pretreatment in series is when the large number of components is brought into contact with the colloidal, aqueous solution in the system tank of the activation stage, the individual components being brought into contact one after the other and thus separated from one another and the components subsequently are fed to the phosphating.
  • the system tank is the container in which the colloidal, aqueous solution is located for the purpose of activation for phosphating in series.
  • organic complexing agents can be used to mask the foreign ions in order to maintain a long bath service life. Ions are added. In this case, it must be considered whether the economic advantage that the activation stage and, if necessary, upstream cleaning stages and rinsing can be operated with process water, is not thwarted by the addition of organic complexing agents and their process-related monitoring in the system tank of the activation stage.
  • Suitable organic complexing agents are selected from ⁇ -hydroxycarboxylic acids, which in turn are preferably selected from gluconic acid, tartronic acid, glycolic acid, citric acid, tartaric acid, lactic acid, very particularly preferably gluconic acid, and / or organophosphonic acids, which in turn are preferably selected are from etidronic acid, aminotris (methylenephosphonic acid), aminotri (methylenphosphonic acid)), phosphonobutane-1, 2,4-tricarboxylic acid, Diethylenetriaminepenta (methylenephosphonic acid), hexamethylenediamine tetra (methylenephosphonic acid) and / or hydroxyphosphonoacetic acid, particularly preferably from etidronic acid.
  • ⁇ -hydroxycarboxylic acids which in turn are preferably selected from gluconic acid, tartronic acid, glycolic acid, citric acid, tartaric acid, lactic acid, very particularly preferably gluconic acid, and / or organophosphonic
  • organic complexing agent should only take place to such an extent that its amount in the colloidal, aqueous solution is preferably not greater than twice, particularly preferably not greater than 1.5 times, based on the amount of alkaline earth metal ions and is very particularly preferably not greater than equimolar to the amount of alkaline earth metal ions.
  • the phosphating can be carried out in a stable manner in the activation stage up to a water hardness corresponding to 10 mmol / l alkaline earth metal ions, that is to say largely without the addition of complexing agents.
  • the colloidal, aqueous solution therefore preferably contains no more than 10 mmol / L, particularly preferably no more than 5 mmol / L, of alkaline earth metal ions dissolved in water.
  • Another advantage of the method according to the invention compared to conventional activation methods is that the addition of condensed phosphates can be dispensed with in the activation stage.
  • Condensed phosphates dissolved in the aqueous phase of activation fulfill the task of masking permanent water hardness on the one hand and, on the other hand, experience has shown the specific task of stabilizing the proportion of phosphates hopeite, phosphophylilite, scholzite and / or hurealite on a colloidal level, especially in the continuous operation of a pretreatment line, and so keep it permanently available for activation. It is remarkable and surprising for the person skilled in the art that in processes according to the invention which are based on an activation stage based on the particulate constituent (a), the addition of condensed phosphates can be dispensed with.
  • the addition of condensed phosphates can be completely dispensed with, so that only those small amounts of condensed phosphates are to be found in the activation that are from upstream cleaning stages with the component to be pretreated, in particular during the treatment a large number of components in series, enter the activation stage.
  • the proportion of condensed phosphates dissolved in water in the colloidal aqueous solution based on the phosphate content of the at least one particulate compound (a1), based on the element P is below 0.25, preferably below 0 .20, particularly preferably below 0.15 and very particularly preferably below 0.10.
  • the proportion of condensed phosphates dissolved in water in the colloidal, aqueous solution, calculated as P, is less than 20 mg / kg, preferably less than 15 mg / kg, particularly preferably less than 10 mg / kg, based on is the colloidal, aqueous solution.
  • condensed phosphates are metaphosphates and polyphosphates, preferably polyphosphates, particularly preferably pyrophosphate.
  • the condensed phosphates are preferably in the form of compounds of monovalent cations, preferably selected from Li, Na and / or K, particularly preferably Na and / or K, before.
  • the proportion of condensed phosphates can be determined analytically from the difference in the total phosphate content in the non-particulate component of the colloidal, aqueous solution with and without oxidative digestion, for example by means of peroxodisulfate, the dissolved orthophosphate proportion being quantified by means of photometry.
  • an enzymatic digestion with a pyrophosphatase can take place instead of the oxidative digestion.
  • the non-particulate component of the colloidal, aqueous solution is the solids content of the colloidal, aqueous solution in the permeate of the previously described ultrafiltration after it has been dried to a constant mass at 105 ° C - i.e. the solids content after separation of the particulate component (a) by means of ultrafiltration.
  • the colloidal, aqueous solution in activation (i) of the method according to the invention preferably has an alkaline pH value, particularly preferably a pH value above 8.0, particularly preferably above 9.0, but preferably below 11.0 , whereby compounds influencing the pH value such as phosphoric acid, sodium hydroxide solution, ammonium hydroxide or ammonia are used to adjust it can.
  • the “pH value”, as used in the context of the present invention, corresponds to the negative decadic logarithm of the hydronium ion activity at 20 ° C. and can be determined using pH-sensitive glass electrodes.
  • the proportion of phosphates contained in the at least one particulate inorganic compound (a1) based on the dispersed particulate component (a) of the colloidal, aqueous solution is preferably at least 25% by weight, particularly preferably at least 35% by weight, particularly preferred at least 40% by weight, very particularly preferably at least 45% by weight.
  • the inorganic particulate constituent of the colloidal, aqueous solution is in turn that which remains when the particulate constituent (a) obtained from the drying of the retentate of the ultrafiltration is placed in a reaction furnace with the supply of a CO 2 -free oxygen stream at 900 ° C without the addition of catalysts or other additives are pyrolysed until an infrared sensor in the outlet of the reaction furnace delivers a signal identical to the C0 2 -free carrier gas (blank value).
  • the phosphates contained in the inorganic particulate constituent are determined as phosphorus content by means of atomic emission spectrometry (ICP-OES) directly from the acid digestion after acid digestion of the same with aqueous 10% by weight HNO 3 solution at 25 ° C for 15 min.
  • ICP-OES atomic emission spectrometry
  • the active components of the colloidal, aqueous dispersion which effectively promote the formation of a closed phosphate coating on the metal surfaces and in this sense activate the metal surfaces, are, as already mentioned, primarily composed of phosphates, which in turn cause the formation of finely crystalline coatings, and are therefore at least partially selected from Hopeite, phosphophyllite, scholzite and / or hureaulite, preferably at least partially selected from hopeite, phosphophyllite and / or scholzite, particularly preferably at least partially selected from hopeite and / or phosphophyllite and very particularly preferably at least partially selected from hopeite.
  • Activation within the meaning of the present invention is therefore essentially based on the phosphates contained in the activation stage in particulate form.
  • hopeite stoichiometrically comprises Zn 3 (P0 4 ) 2 as well as the nickel and manganese-containing variants Zn 2 Mn (P0 4 ) 3 , Zn 2 Ni (P0 4 ) 3
  • phosphophyllite from Zn 2 Fe (P04) 3 Scholzite consists of Zn2Ca (P04) 3 and Hureaulite consists of Mh 3 (R04) 2.
  • the aqueous dispersion according to the invention can after separation of the particulate component (a) by means of ultrafiltration with a nominal exclusion limit of 10 kD (NMWC, Nominal Molecular Weight Cut Off) as described above and drying of the retentate to constant mass at 105 ° C by means of X-ray diffraction methods (XRD) be detected.
  • NMWC Nominal Molecular Weight Cut Off
  • phosphates which comprise zinc ions and have a certain crystallinity
  • the proportion of the dispersed particulate component (a) of the colloidal, aqueous solution is at least 0.05 g / kg, preferably at least 0.1 g / kg, particularly preferably at least 0.2 g / kg, but preferably is not greater than 10 g / kg, particularly preferably not greater than 2 g / kg, very particularly preferably not greater than 1 g / kg in each case based on the colloidal, aqueous solution.
  • the proportion of titanium in the inorganic particulate component of the colloidal, aqueous solution is therefore less than 0.01% by weight, particularly preferably less than 0.001% by weight, based on the colloidal, aqueous solution.
  • the colloidal, aqueous solution of activation (i) contains a total of less than 10 mg / kg, particularly preferably less than 1 mg / kg, of titanium.
  • the activation stage in the method according to the invention can additionally be characterized by its D50 value, above which the activation performance decreases significantly.
  • the D50 value of the colloidal, aqueous solution is preferably below 1 pm, particularly preferably below 0.4 pm.
  • the D50 value denotes the particle diameter which does not exceed 50% by volume of the particulate constituents contained in the colloidal, aqueous solution.
  • the polymeric organic compounds (a2) which are used as dispersants and which have polyoxyalkylene units are, for the purposes of the present invention, at least partially composed of styrene and / or an ⁇ -olefin with not more than 5 carbon atoms and of maleic acid, its anhydride and / or its imide, and cause the extremely high stability of the colloidal, aqueous solution in the activation stage of the process according to the invention.
  • the ⁇ -olefin is preferably selected from ethene, 1-propene, 1-butene, isobutylene, 1-pentene, 2-methyl-1-butene and / or 3-methyl-1-butene and is particularly preferably selected from isobutylene. It is clear to the person skilled in the art that the polymeric organic compounds (a2) contain these monomers as structural units in unsaturated form with one another or with other structural units covalently linked.
  • Suitable commercially available representatives are, for example, Dispex® CX 4320 (BASF SE) a maleic acid-isobutylene copolymer modified with polypropylene glycol, Tego® Dispers 752 W (Evonik Industries AG) a maleic acid-styrene copolymer modified with polyethylene glycol or Edaplan® 490 (Münzing Chemie GmbH) modified a maleic acid-styrene copolymer with EO / PO and imidazole units.
  • those polymeric organic compounds (a2) which are at least partly composed of styrene are preferred.
  • the polymeric organic compounds (a2) used as dispersing auxiliaries have polyoxyalkylene units which are preferably composed of 1,2-ethanediol and / or 1,2-propanediol, particularly preferably both 1,2-ethanediol and 1,2 Propanediol, the proportion of 1,2-propanediols in the total of the polyoxyalkylene units being preferably at least 15% by weight, but particularly preferably not exceeding 40% by weight, based on the total of the polyoxyalkylene units.
  • the polyoxyalkylene units are preferably contained in the side chains of the polymeric organic compounds (a2).
  • a proportion of the polyoxyalkylene units in the totality of the polymeric organic compounds (a2) of preferably at least 40% by weight, particularly preferably at least 50% by weight, but preferably not more than 70% by weight is advantageous for the Dispersibility.
  • the organic polymeric compounds (a2) contain preferably also N-heterocycle units, which in turn are preferably selected from pyridine, imidazole, imidazoline, morpholine, pyrrole and / or pyrrolidone units, particularly preferably from imidazole and / or imidazoline units, in particular preferably from imidazole units.
  • N-heterocycle units are each preferably part of the side chains of the polymeric organic compound (a2) and, within the side chain, are preferably aliphatically connected to the main chain via preferably at least 3 carbon atoms, particularly preferably in such a way that the polyoxyalkylene units of the polymeric organic compounds (a2 ) are at least partially end-group-capped with an N-heterocycle, so that in the preferred embodiment there are terminal N-heterocyclic groups in the polyoxyalkylene side chain.
  • the covalent linkage of the N-heterocycle units in the side chains of the polymeric organic compound (a2), preferably the side chains which have polyoxyalkylene units, is preferably carried out via a nitrogen atom of the heterocycle.
  • the N-heterocycle units are preferably at least partially quaternized, particularly preferably as N-alkylated quaternary N-heterocycle units.
  • the amine number of the organic polymeric compounds (a2) is at least 25 mg KOH / g, particularly preferably at least 40 mg KOH / g, but preferably less than 125 mg KOH / g, particularly preferably less than 80 mg KOH / g, so that in a preferred embodiment, the All of the polymeric organic compounds in the particulate constituent (a) have these preferred amine numbers.
  • the amine number is determined on the basis of a weight of about 1 g of the respective reference value - organic polymeric compounds (a2) or totality of the polymeric organic compounds in the particulate component - in 100 ml of ethanol, with 0.1 N HCl standard solution against the indicator Bromophenol blue is titrated until the color changes to yellow at a temperature of the ethanolic solution of 20 ° C.
  • the amount of standard solution HCl consumed in milliliters multiplied by the factor 5.61 divided by the exact weight of the initial weight in grams corresponds to the amine number in milligrams of KOH per gram of the respective reference value.
  • the presence of maleic acid, insofar as it is a constituent of the organic polymeric compound (a2) in the form of the free acid and not in the form of the anhydride or imide, can impart increased water solubility of the dispersing aid, especially in the alkaline range. It is therefore preferred that the polymeric organic compounds (a2), preferably also all of the polymeric organic compounds in the particulate component (a), have an acid number according to DGF CV 2 (06) (as of April 2018) of at least 25 mg KOH / g have, but preferably less than 100 mg KOH / g, particularly preferably less than 70 mg KOH / g, in order to ensure a sufficient number of polyoxyalkylene units.
  • the polymeric organic compounds (a2) preferably also all of the polymeric organic compounds in the particulate component (a), have a hydroxyl number of less than 15 mg KOH / g, particularly preferably less than 12 mg KOH / g, particularly preferably less than 10 mg KOH / g, each determined according to method A of 01/2008: 20503 from European Pharmacopoeia 9.0.
  • the proportion of the polymeric organic compounds (a2), preferably all of the polymeric organic compounds in the particulate component (a), based on the particulate component (a ) is at least 3% by weight, particularly preferably at least 6% by weight, but preferably does not exceed 15% by weight.
  • the present invention relates to a method for anti-corrosive pretreatment based on phosphating with the inclusion of an aqueous dispersion.
  • a method according to the invention relates to Corrosion-protecting pretreatment of a metallic material selected from zinc, iron or aluminum or a component that is at least partially composed of such metallic materials, in which the metallic material or the component is first activated (i) and then phosphated (ii) in successive process steps , in particular zinc phosphating, the activation in process step (i) being carried out by bringing the metallic material or at least one metallic material of the component into contact with a colloidal, aqueous solution as described above, which is available as a Aqueous dispersion diluted by a factor of 20 to 100,000 comprising: based on the aqueous dispersion at least 5% by weight of a dispersed particulate constituent (A), which in turn
  • (A1) at least one particulate inorganic compound which is composed of phosphates of polyvalent metal cations at least partially selected from hopeite, phosphophyllite, scholzite and / or hureaulite,
  • (A2) at least one polymeric organic compound which is at least partly composed of styrene and / or an ⁇ -olefin having not more than 5 carbon atoms and at least partly composed of maleic acid, its anhydride and / or its imide, the polymeric organic compound additionally has polyoxyalkylene units, and optionally at least one thickener (B), which is preferably selected from urea urethane resins, particularly preferably from urea urethane resins which have an amine number of less than 8 mg KOH / g, preferably less than 5 mg KOH / g, particularly preferably less than 2 mg KOH / g, the dilution being carried out with water which is at least 0.5 mmol / L, preferably at least 1 mmol / L, particularly preferably at least 1.5 mmol / l in water dissolved alkaline earth metal ions, but preferably not more than 10 mmol / L, particularly preferably not more than 6 mmol / L of
  • the dispersed particulate constituent (A) and the at least one particulate inorganic compound (A1) or polymeric organic compound (A2) the same definitions and preferred specifications apply as were given above for the colloidal, aqueous solution.
  • the dilution is preferably carried out with deionized water (K ⁇ IpScnr 1 ), particularly preferably with service water, in order to make the process according to the invention as resource-saving as possible.
  • Process water in the light of the underlying technical application contains at least 0.5 mmol / L of alkaline earth metal ions.
  • a thickener according to component (B) gives the aqueous dispersion, in combination with its particulate constituent, a thixotropic flow behavior and thus contributes to counteracting the irreversible formation of agglomerates in the particulate constituent of the dispersion, from which primary particles can no longer be removed.
  • the addition of the thickener should preferably be controlled so that the aqueous dispersion has a maximum dynamic viscosity in the shear rate range of 0.001 to 0.25 reciprocal seconds at a temperature of 25 ° C.
  • the viscosity over the specified shear rate range can be determined using a plate / cone viscometer with a cone diameter of 35 mm and a gap width of 0.047 mm.
  • K ⁇ IpScnr 1 deionized water
  • the mixture with water is to be made up in such a way that the appropriate amount of the polymeric chemical compound is added to the water phase with stirring at 25 ° C and the homogenized mixture is then freed of air bubbles in an ultrasonic bath and left to stand for 24 hours.
  • An aqueous dispersion according to the invention preferably contains a total of at least 0.5% by weight, but preferably not more than 4% by weight, particularly preferably not more than 3% by weight, of one or more thickeners according to component (B), further preferred the total proportion of polymeric organic compounds in the non-particulate component of the aqueous dispersion does not exceed 4% by weight (based on the dispersion).
  • the non-particulate constituent is the solids content of the aqueous dispersion in the permeate of the ultrafiltration already described after it has been dried to a constant mass at 105 ° C. - i.e. the solids content after the particulate constituent has been separated off by means of ultrafiltration.
  • the thickener according to component (B) is initially preferably selected from polymeric organic compounds, which in turn are preferably selected from polysaccharides, cellulose derivatives, aminoplasts, polyvinyl alcohols, polyvinylpyrrolidones, polyurethanes and / or urea urethane resins, and particularly preferably from urea urethane resins.
  • a urea urethane resin as a thickener according to component (B) of the preferred method according to the invention for providing a colloidal, aqueous solution based on the aqueous dispersion is a mixture of polymeric compounds that result from the reaction of a polyvalent isocyanate with a polyol and a mono- and / or diamine emerges.
  • the urea urethane resin is made from a polyvalent isocyanate, preferably selected from 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2 (4), 4-trimethyl-1,6-hexamethylene diisocyanate, 1, 10-decamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate and mixtures thereof, p- and m-xylylene diisocyanate, and 4-4 ', - Diisocyanatodicyclohexylmethane, particularly preferably selected from 2,4-toluene diisocyanate and / or m-xylylene diisocyanate.
  • a polyvalent isocyanate preferably selected from 1,4-tetram
  • the urea urethane resin is derived from a polyol selected from polyoxyalkylene diols, particularly preferably from polyoxyethylene glycols, which in turn are preferably composed of at least 6, particularly preferably at least 8, particularly preferably at least 10, but preferably less than 26, particularly preferably less than 23 oxyalkylene units.
  • urea urethane resins are obtainable by a first reaction of a diisocyanate, for example toluene-2,4-diisocyanate, with a polyol, for example a polyethylene glycol, to form NCO-terminated urethane prepolymers, after which with a primary monoamine and / or with a primary diamine, for example m-xylylenediamine, is reacted further.
  • a diisocyanate for example toluene-2,4-diisocyanate
  • a polyol for example a polyethylene glycol
  • NCO-terminated urethane prepolymers after which with a primary monoamine and / or with a primary diamine, for example m-xylylenediamine, is reacted further.
  • Urea urethane resins which have neither free nor blocked isocyanate groups are particularly preferred.
  • Such urea urethane resins as a component of the aqueous dispersion from which the colloidal, aqueous solution of the process according to the invention is obtainable by dilution, promote the formation of loose agglomerates of primary particles, which, however, are stabilized in the aqueous phase and protected against further agglomeration to such an extent that the sedimentation of the particulate constituent in the aqueous dispersion is largely prevented.
  • urea urethane resins which have neither free or blocked isocyanate groups nor terminal amine groups are preferably used as component (B).
  • the thickener according to component (B), which is a urea urethane resin therefore has an amine number of less than 8 mg KOH / g, particularly preferably less than 5 mg KOH / g, particularly preferably less than 2 mg KOH / g, each determined by the method as described above for the organic polymeric compound (A2).
  • an aqueous dispersion is accordingly suitable for providing the colloidal, aqueous solution of activation preferred, in which the totality of the polymeric organic compounds in the non-particulate component preferably has an amine number of less than 16 mg KOH / g, particularly preferably less than 10 mg KOH / g, particularly preferably less than 4 mg KOH / g.
  • the urea urethane resin has a hydroxyl number in the range from 10 to 100 mg KOH / g, particularly preferably in the range from 20 to 60 mg KOH / g, determined according to method A of 01/2008: 20503 from European Pharmacopoeia 9.0. having.
  • a weight-average molar mass of the urea urethane resin in the range from 1000 to 10000 g / mol, preferably in the range from 2000 to 6000 g / mol is advantageous according to the invention and therefore preferred, in each case determined experimentally as above in connection with the definition of a polymeric compound according to the invention described.
  • the pH of the dispersion for providing the colloidal, aqueous solution for activating the method according to the invention is usually in the range from 6.0-9.0 and such a pH range is therefore preferred according to the invention.
  • the pH of the aqueous dispersion possibly also by adding alkaline compounds, is above 7.2, particularly preferably above of 8.0.
  • the alkalinity of the aqueous dispersion according to the invention is, since some polyvalent metal cations have amphoteric character and can therefore be leached out of the particulate constituent at higher pH values, ideally limited, so that the pH value of the aqueous dispersion is preferably below 10 and particularly is preferably below 9.0.
  • the aqueous dispersion described above for providing the colloidal, aqueous solution is in turn preferably obtainable by i) providing a pigment paste by triturating 10 parts by mass of an inorganic particulate compound (A1) with 0.5 to 2 parts by mass of the polymeric organic compound (A2) in the presence from 4 to 7 parts by mass of water and grinding until a D50 value of less than 1 pm is reached, determined by means of dynamic light scattering after dilution with water by a factor of 1000, for example by means of Zetasizer® Nano ZS, Malvern Panalytical GmbH; ii) Diluting the pigment paste with such an amount of water, preferably deionized water (K ⁇ 1pScnr 1 ) or industrial water, and a thickener (B) that a dispersed particulate component (A) of at least 5 wt .-% and a maximum dynamic Viscosity of at least 1000 Pa s at a temperature of 25 ° C in the shear rate range of
  • the aqueous dispersion can also contain auxiliaries, for example selected from preservatives, wetting agents and defoamers, which are contained in the amount necessary for the respective function.
  • auxiliaries for example selected from preservatives, wetting agents and defoamers, which are contained in the amount necessary for the respective function.
  • the proportion of auxiliaries, particularly preferably of other compounds in the non-particulate constituent, which are not thickeners or compounds with an alkaline reaction, is preferably less than 1% by weight.
  • an alkaline compound is water-soluble (water solubility: at least 10 g per kilogram of water with K ⁇ 1 pScnr 1 ) and has a pK ⁇ value for the first protonation stage above 8.0.
  • a metallic material selected from zinc, iron or aluminum this includes all materials which contain more than 50 at% of the respective element.
  • Anticorrosive pretreatment always affects the surfaces of the material or component.
  • the material can be a uniform material or a coating.
  • galvanized steel types consist of both the material steel and the material zinc, whereby surfaces of iron can be exposed at the cut edges and sanded-through points, for example of an automobile body made of galvanized steel, and according to the invention, the material iron is then pretreated.
  • the components treated according to the present invention can be any shape and design spatial structures that originate from a manufacturing process, in particular also semi-finished products such as strips, sheets, rods, tubes, etc. and composite structures assembled from the aforementioned semi-finished products, the semi-finished products preferably being glued, Welding and / or flanging are connected to form a composite structure.
  • a rinsing step can take place between activation (i) and phosphating (ii) in order to reduce the carryover of alkaline constituents into the mostly acidic phosphating, but a rinsing step is preferably dispensed with in order to fully maintain the activation performance.
  • a rinsing step is used exclusively for the complete or partial removal of soluble residues, particles and active components, which are carried away adhering to the component from a previous wet chemical treatment step, from the component to be treated, without active components based on metallic or semi-metallic elements being contained in the rinsing liquid itself, the are used up just by bringing the metallic surfaces of the component into contact with the flushing liquid.
  • the rinsing liquid can only be city water or deionized water or, if necessary, can also be a rinsing liquid which contains surface-active compounds to improve the wettability with the rinsing liquid.
  • the phosphating in process step (ii) by bringing the surfaces into contact with an acidic aqueous composition containing 5-50 g / kg of phosphates dissolved in water calculated as PO4 and preferably additionally contains at least one source of free fluoride.
  • the amount of phosphate ions includes orthophosphoric acid and the anions of the salts of orthophosphoric acid, which are dissolved in water, calculated as PO4.
  • the subsequent phosphating is zinc phosphating and the phosphating in process step (ii) is based on an acidic aqueous composition containing 0.3-3 g / kg of zinc ions, preferably on an acidic aqueous composition containing 5 - 50 g / l of phosphate ions, 0.3 - 3 g / l of zinc ions and a lot of free fluoride.
  • a source of free fluoride ions is essential for the process of layer-forming zinc phosphating, insofar as the layer formation is desired on all metallic materials selected from zinc, iron or aluminum and, for example, necessary for the zinc phosphating of automobile bodies, which are at least partially also made of aluminum . If all surfaces of the metallic materials of a component are to be provided with a phosphate coating, the amount of particulate constituents in the activation often has to be adapted to the amount of free fluoride required for the formation of a layer in the zinc phosphating.
  • a closed and defect-free phosphate coating if the amount of free fluoride in the acidic aqueous composition is at least 0.5 mmol / kg.
  • the component also made of the metallic material aluminum and should that Surfaces are also provided with a closed phosphate coating it is further preferred in the method according to the invention that the amount of free fluoride in the acidic aqueous composition is at least 2 mmol / kg.
  • the concentration of free fluoride should not exceed values above which the phosphate coatings predominantly have adhesions that can be easily wiped off, since these cannot be avoided even by a disproportionately increased amount of particulate components in the colloidal, aqueous solution of activation. It is therefore also advantageous and therefore preferred for economic reasons if, in the process according to the invention, based on activation (i) followed by zinc phosphating (ii), the concentration of free fluoride in the acidic aqueous composition of zinc phosphating is below 15 mmol / kg, in particular is preferably below 10 mmol / kg and particularly preferably below 8 mmol / kg.
  • Suitable sources for free fluoride are hydrofluoric acid and its water-soluble salts, such as ammonium bifluoride and sodium fluoride, and complex fluorides of the elements Zr, Ti and / or Si, in particular complex fluorides of the element Si.
  • the source of free fluoride in a phosphating according to the present invention is therefore preferably selected from hydrofluoric acid and its water-soluble salts and / or complex fluorides of the elements Zr, Ti and / or Si.
  • Hydrofluoric acid salts are water-soluble for the purposes of the present invention if their solubility in deionized water (K ⁇ IpScnr 1 ) at 60 ° C is at least 1 g / L, calculated as F.
  • the source of free fluoride is at least partially selected from complexes Fluorides of the element Si, in particular from hexafluorosilicic acid and its salts.
  • Speck formation is understood by those skilled in the art of phosphating as the phenomenon of local deposition of amorphous, white zinc phosphate in an otherwise crystalline phosphate layer on the treated zinc surfaces or on the treated galvanized or alloy-galvanized steel surfaces. The formation of specks is caused by a locally increased pickling rate of the substrate.
  • the concentration of silicon dissolved in water in the acidic aqueous composition of the zinc phosphating in process step (ii) is at least 0.5 mmol / kg, particularly preferably at least 1 mmol / kg, particularly preferably at least 2 mmol / kg is, however, preferably less than 15 mmol / kg, particularly preferably less than 12 mmol / kg, particularly preferably less than 10 mmol / kg and very particularly preferably less than 8 mmol / kg.
  • the upper limits for the concentration of silicon are preferred, since above these values phosphate coatings are favored, which predominantly have loose adhesions which cannot be avoided even by a disproportionately increased amount of particulate constituents in the colloidal, aqueous solution of the activation stage.
  • concentration of silicon in the acidic aqueous composition dissolved in water is to be determined in the filtrate of a membrane filtration of the acidic aqueous composition, which was carried out using a membrane with a nominal pore size of 0.2 ⁇ m, by means of atomic emission spectrometry (ICP-OES).
  • the proportion of particulate constituents that contribute to activation must be adapted to the amount of free fluoride and silicon in the zinc phosphating in order to ensure that the layer-forming phosphating on components includes aluminum as a metallic material
  • the higher contents of free fluoride contained in the phosphating bath do not have a detrimental effect on the layer formation, which is of great importance for a constant quality of the phosphate coatings, especially when pretreating a large number of components.
  • a method is preferred according to the invention in which a series of components is to be pretreated, which comprises components that are at least partially made of the materials zinc and aluminum, in which the components of the series are activated one after the other in successive process steps (i) and then subjected to zinc phosphating (ii), the activation in process step (i) being carried out by bringing the component into contact with a colloidal, aqueous solution as described above, which in a preferred embodiment is obtainable as a factor of 20 up to 100,000 diluted previously described aqueous dispersion, and containing the zinc phosphating in process step (ii) by bringing into contact with an acidic aqueous composition
  • At least one source of free fluoride takes place, the quotient of the concentration of the phosphates in the inorganic particulate component of the colloidal, aqueous solution of activation in mmol / kg based on PO4 to the sum of the concentration of free fluoride and the concentration Silicon in each case in the acidic aqueous composition of the zinc phosphating and in each case in mmol / kg is greater than 0.2, preferably greater than 0.3, particularly preferably greater than 0.4.
  • the preferred pH value of the acidic aqueous composition causing the zinc phosphating is above 2.5, particularly preferably above 2.7, but preferably is below 3.5, particularly preferably below 3.3.
  • the proportion of the free acid in points in the acidic aqueous composition of the zinc phosphating in process step (ii) is preferably at least 0.4, but preferably not more than 3.0, particularly preferably not more than 2.0.
  • the percentage of free acid in points is determined by diluting the 10 ml sample volume of the acidic aqueous composition to 50 ml and titrating it with 0.1 N sodium hydroxide solution up to a pH of 3.6. The consumption of ml sodium hydroxide solution indicates the number of free acid points.
  • the usual additives for zinc phosphating can also be carried out in an analogous manner within the scope of the present invention, so that the acidic aqueous composition in process step (ii) uses the usual accelerators such as hydrogen peroxide, nitrite, hydroxylamine, nitroguanidine and / or N-methylmorpholine-N-oxide and can also contain cations of the metals manganese, calcium and / or iron in the form of water-soluble salts, which have a positive influence on the layer formation.
  • a total of less than 10 ppm of nickel and / or cobalt ions are contained in the acidic aqueous composition of the zinc phosphating in process step (ii).
  • a good paint primer is achieved for a subsequent dip painting, in the course of which an essentially organic top layer is applied.
  • a dip painting particularly preferably an electrodeposition painting, particularly preferably a cathodic electrodeposition painting, which is preferably used in addition to the dispersed resin, which is preferably an amine modified polyepoxide includes water-soluble or water-dispersible salts of yttrium and / or bismuth.
  • Table 1 summarizes the results of the zinc phosphating in terms of layer weight and after aging in the corrosion test. It turns out that when the activation is started with city water (B) compared to a start with deionized water (A) homogeneous, closed zinc phosphate coatings with a lower layer weight and also improved corrosion protection results can be achieved.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Materials Engineering (AREA)
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Abstract

L'invention concerne un procédé de phosphatation de surfaces métalliques de manière à former des couches au moyen d'une solution aqueuse colloïdale comme étape d'activation, contenant un constituant particulaire dispersé, en plus des composés inorganiques dispersés de phosphates de cations métalliques polyvalents, le constituant particulaire contient des composés organiques polymères en tant que dispersants, qui sont composés au moins en partie de styrène et/ou d'une alpha-oléfine n'ayant pas plus de 5 atomes de carbone et comportant au moins partiellement de l'acide maléique et/ou de l'anhydride et/ou de l'imide de celui-ci, et les composés organiques polymères comprennent en outre des unités polyoxyalkylène. Les étapes de nettoyage et de rinçage précédant l'étape d'activation ainsi que l'étape d'activation elle-même peuvent être réalisées de manière économe en ressources à l'aide d'eau de service sans perte de performance d'activation en ce que la solution aqueuse colloïdale contient au moins 0,5 mmol/l d'ions métalliques alcalino-terreux dissous dans l'eau.
PCT/EP2020/082618 2019-11-26 2020-11-19 Procédé d'économie de ressources pour activer une surface métallique avant un processus de phosphatation WO2021104976A1 (fr)

Priority Applications (6)

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JP2022531060A JP2023505069A (ja) 2019-11-26 2020-11-19 リン酸塩処理前に金属表面を活性化するための省資源方法
CN202080081532.6A CN114729457B (zh) 2019-11-26 2020-11-19 用于在磷化前活化金属表面的资源节约型方法
EP20807405.4A EP4065749B1 (fr) 2019-11-26 2020-11-19 Procédé économe en ressources permettant d'activer une surface métallique avant une phosphatation
MX2022006302A MX2022006302A (es) 2019-11-26 2020-11-19 Metodo de ahorro de recursos para activar una superficie metalica antes del fosfatado.
KR1020227017348A KR20220106125A (ko) 2019-11-26 2020-11-19 포스페이팅 전에 금속 표면을 활성화하기 위한 자원 절감 방법
US17/664,665 US20220282381A1 (en) 2019-11-26 2022-05-24 Resource-saving method for activating a metal surface prior to phosphating

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EP19211407.2A EP3828307A1 (fr) 2019-11-26 2019-11-26 Procédé économe en ressources permettant d'activer une surface métallique avant une phosphatation
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EP4174211A1 (fr) * 2021-11-02 2023-05-03 Henkel AG & Co. KGaA Traitement en plusieurs étages permettant d'activer le phosphatation au zinc des composants métalliques pourvus de surfaces en zinc

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US20150064445A1 (en) * 2013-09-05 2015-03-05 Ppg Industries Ohio, Inc. Activating rinse and method for treating a substrate
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DE102005059314B4 (de) * 2005-12-09 2018-11-22 Henkel Ag & Co. Kgaa Saure, chromfreie wässrige Lösung, deren Konzentrat, und ein Verfahren zur Korrosionsschutzbehandlung von Metalloberflächen
JP5166157B2 (ja) * 2008-07-29 2013-03-21 日本曹達株式会社 無機系粒子水性分散液およびその製造方法
MX355473B (es) * 2010-09-10 2018-04-19 Chemetall Gmbh Star Método para recubrir superficies metálicas con un agente de recubrimiento que contiene un polímero, el agente de recubrimiento y uso del mismo.
US20170306497A1 (en) * 2016-04-25 2017-10-26 Ppg Industries Ohio, Inc. System for nickel-free zinc phosphate pretreatment
EP3392376A1 (fr) * 2017-04-21 2018-10-24 Henkel AG & Co. KGaA Procédé formant des couches de phosphatate de zinc sur des composants métalliques en série
EP3954805A1 (fr) * 2020-08-11 2022-02-16 Henkel AG & Co. KGaA Procédé efficace dans l'utilisation des ressources destiné à la phosphatation au zinc d'une surface métallique
EP3964606A1 (fr) * 2020-09-04 2022-03-09 Henkel AG & Co. KGaA Procédé en une étape de phosphation du zinc

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WO1998039498A1 (fr) 1997-03-07 1998-09-11 Henkel Corporation Conditionnement de surfaces metalliques prealablement a la phosphatation
EP1566466A1 (fr) * 2004-02-20 2005-08-24 Nippon Paint Co., Ltd. Composition et procédé de conditionnement de surfaces
US20150064445A1 (en) * 2013-09-05 2015-03-05 Ppg Industries Ohio, Inc. Activating rinse and method for treating a substrate
WO2019238573A1 (fr) * 2018-06-11 2019-12-19 Henkel Ag & Co. Kgaa Dispersion aqueuse pour l'activation d'une surface métallique et son procédé de phosphatation

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CN114729457A (zh) 2022-07-08
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EP3828307A1 (fr) 2021-06-02
JP2023505069A (ja) 2023-02-08
US20220282381A1 (en) 2022-09-08
CN114729457B (zh) 2024-04-30
EP4065749A1 (fr) 2022-10-05

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