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
  • C23C22/34—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

Definitions

• the present invention relates to the use of an adhesion-promoting organic compound having at least one tertiary amine group which is in turn connected via a bridging divalent radical to the carbonyl carbon atom of an amide group, wherein the bridging divalent radical is two
• the present invention comprises a method for
• the invention relates to a metallic substrate having a mixed organic-inorganic coating consisting of oxides, hydroxides and / or oxyfluorides of the elements Zr, Ti and / or Si and the adhesion-promoting organic compounds.
• 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 a metal pretreatment are known, which are aimed either at an additive to the conversion of the metal surfaces by a pickling attack causing agents or at a multi-stage conditioning of the metal surface.
• organic compounds are often additized or applied in a subsequent conversion step of the conversion treatment, which are to take over the function of a coupling agent and for this purpose have certain chemical functionalities that provide a chemical interaction with the organic constituents of the paint coating in view.
• EP 1 433 877 A1 teaches the addition of a chromium-free acidic aqueous composition based on the elements Zr, Ti and / or Hf
• EP 1 455 002 A1 again shows in one aspect the positive effect of polymers based on vinyl and allylamines for the corrosion protection effect.
• DE 100 05 1 13 A1 describes the positive effect of homo- and / or copolymers of vinylpyrrolidone, in particular of copolymers of vinylpyrrolidone with additional caprolactam groups, in the treatment of bare metal surfaces for a subsequent coating.
• the object was to further standardize the anti-corrosive properties of conversion layers on different metal substrates obtainable by pretreatment with compositions of water-soluble compounds of the elements Zr, Ti and / or Si and in particular to improve the steel surfaces.
• the average undermigration values in the corrosive delamination after coating layer build-up should be improved.
• a small variance in the conversion layer should result, that is to say a reproducible conversion of the process technology
• Metal surface can be achieved. Furthermore, a higher tolerance to increased treatment times, as occurs regularly, for example in the case of temporary plant shutdown of a pretreatment line despite automation for maintenance purposes or due to manufacturing, is desirable. In conventional pretreatment baths, which cause a conversion of the metal surfaces based on the elements Zr, Ti and / or Si, deterioration of the corrosion protection properties occurs during prolonged exposure in the pretreatment bath despite increased layer coverage. Regarding the application on different materials
• Metal substrates in particular, an optimal corrosion protection effect of such composite structures by means of a corresponding wet-chemical pretreatment is desired, which in addition to surfaces of the material iron and / or steel and surfaces of at least one of the materials zinc, galvanized steel and / or aluminum.
• This object is achieved in a first aspect of the present invention by an acidic aqueous composition for the anticorrosive pretreatment of
• a compound of the elements Zr, Ti and / or Si according to component (A) is water-soluble, if their solubility in deionized water ( ⁇ ⁇ 1 ⁇ 3 ⁇ 1 ) at 20 ° C at least
• the first aspect of the present invention is one for forming a
• Conversion layer containing sufficient amount of active components in the acidic aqueous composition certainly when at least one of the elements Zr, Ti or Si in the form of compounds according to component (A) with at least 0.005 g / kg calculated as Zr is included, so that such a minimum proportion is preferred.
• the total proportion of compounds of component (A) based on the elements Zr, Ti and Si is preferably not greater than 1 g / kg, particularly preferably not greater than 0.5 g / kg, particularly preferably not greater than 0.3 g / kg, since higher contents are usually the No further improve the corrosion-protective properties of the conversion layer, but due to the higher deposition kinetics make it difficult to control the coating layer with respect to these elements.
• Suitable representatives of the water-soluble compounds of the elements Zr, Ti or Si according to component (A) are compounds which in aqueous solution in anions of
• Fluorocomplexes dissociate.
• Such preferred compounds are, for example, H 2 ZrF 6, K 2 ZrF 6, Na2ZrF 6 and (NFU ⁇ ZrFe and the analogous titanium and silicon compounds.
• fluorine-free compounds of the elements Zr, Ti or Si, in particular of the elements Zr or Ti can be used as water-soluble compounds according to the invention, for example (NH 4) 2Zr (OH) 2 (C0 3 ) 2 or TIC SC) or silanes having at least one covalent Si-0 bond.
• an acidic composition according to the invention contains a source of fluoride ions, which is required for a homogeneous and reproducible conversion of the
• the source of fluoride ions is any inorganic compound capable of dissolving or dispersing in water to liberate fluoride ions.
• a preferred source of fluoride ions are complex or simple fluorides. Simple fluorides are understood to mean hydrofluoric acid and its salts, such as alkali fluorides, ammonium fluoride or ammonium bifluoride, whereas complex fluorides are coordination compounds according to the invention in which fluorides are coordinated as ligands of one or more central atoms. Accordingly, preferred representatives of the complex fluorides are the aforementioned fluorine-containing complex compounds of the elements Zr, Ti or Si.
• the proportion of components (B) which are a source of fluoride ions in the acidic aqueous composition is preferably at least such that an amount of free fluoride of at least 0.005 g / kg, preferably of at least 0.01 g / kg but preferably not more than 0.4 g / kg, more preferably not more than 0.1 g / kg in the acidic aqueous composition.
• the free fluoride content is determined by means of calibrated fluoride-sensitive electrode directly in the acidic aqueous composition at 20 ° C.
• component (B) for optimum conversion of a metal surface, in particular those of the material iron, by contacting with an acidic aqueous composition according to the invention, it is preferred for component (B) to be present in an amount such that the molar ratio of total fluoride content to the total amount of components (A) based on the elements Zr, Ti and Si is greater than 4.5, preferably greater than 5.0, more preferably greater than 5.5.
• the total fluoride content is determined with a fluoride-sensitive electrode in a TISAB-buffered aliquot of the acidic aqueous composition at 20 ° C (TISAB: "Total Lonic Strength Adjustment Buffer”), wherein the volume-related mixing ratio of buffer to the aliquot part of the acidic aqueous
• TISAB buffer is prepared by dissolving 58 g of NaCl, 1 g of sodium citrate and 50 ml of glacial acetic acid in 500 ml of deionized water ( ⁇ ⁇ Scm -1 ) and setting a pH of 5.3 by means of 5 N NaOH and make up to a total volume of 1000 ml again with deionized water
• the acidic aqueous composition for accelerating the conversion of the metal surfaces which are contacted with the composition additionally contains at least one water-soluble compound (D) which is a source of copper ions, preferably in the form of a water-soluble salt.
• D water-soluble compound
• copper ions for example, copper sulfate, copper nitrate and copper acetate.
• the presence of copper ions is also beneficial for the anti-corrosive properties of the resulting on the surfaces of the metal materials in the course of the conversion
• the content of copper ions from water-soluble compounds (D) in the acidic aqueous composition for this purpose is preferably at least 0.001 g / kg, more preferably at least 0.005 g / kg.
• the content of copper ions is preferably not more than 0.1 g / kg, more preferably not more than 0.05 g / kg, because otherwise the deposition of elemental copper over the
• the acidic aqueous composition additionally contains at least one water-soluble compound (E) having a standard reduction potential at pH 0 above +0.6 V (SHE), and is preferably selected from inorganic nitrogen compounds, more preferably from nitric acid and / or nitrous acid and their salts.
• the proportion of water-soluble compounds (E) is for accelerating the conversion layer formation preferably at least 0.001 mol / L, preferably at least 0.01 mol / L, but for reasons of economy, preferably at less than 0.2 mol / L.
• the method is characterized by its high tolerance to zinc ions, which necessarily accumulate in the treatment of galvanized steel in the pre-treatment bath. It has also been shown that the presence of zinc ions has an advantageous effect on the conversion layer structure, so that in inventive
• Compositions are preferably additionally contained as component (F) zinc ions, preferably at least 0.1 g / kg of zinc ions, more preferably at least 0.3 g / kg of zinc ions, but preferably not more than 3 g / kg on zinc ions.
• component (F) zinc ions preferably at least 0.1 g / kg of zinc ions, more preferably at least 0.3 g / kg of zinc ions, but preferably not more than 3 g / kg on zinc ions.
• the pH of the acidic aqueous composition of the invention is
• the bridging divalent radical covalently bonds a tertiary amine group to the carbonyl carbon atom of an amide group, the bridging divalent radical being composed of two carbon atoms as bridging atoms is.
• a bridging atom in connection with compounds according to component (C) is always an atom which is part of the shortest chain of covalently bonded atoms which connects the tertiary amine group to the carbonyl carbon atom of the amide group.
• the substitution of the bridge atoms is not limited to particular radicals, but the bridging atoms are preferably independently substituted with radicals selected from hydrogen, branched or unbranched aliphatics having not more than 6 carbon atoms, alkylcarboxylic acids having not more than 5 carbon atoms or having such divalent aliphatic radicals at least 3, but not more than 5 carbon atoms substituted, which connect the two bridge atoms together.
• radicals selected from hydrogen, branched or unbranched aliphatics having not more than 6 carbon atoms, alkylcarboxylic acids having not more than 5 carbon atoms or having such divalent aliphatic radicals at least 3, but not more than 5 carbon atoms substituted, which connect the two bridge atoms together.
• compositions in particular bring about a further standardization of the conversion layer formation on different metallic materials in such a way that the anticorrosive performance remains stable over a wide application period and defects in the
• Plant standstill in the pre-treatment line does not mean that the bodies, which were exposed to a significantly longer treatment time, must be discharged.
• compositions are also important for opening a suitable time window in the pretreatment of components composed of different materials in composite construction, since different materials usually have a different minimum treatment time to set an optimal
• the adhesion promoter according to component (C) additionally contains at least one secondary amine group which has at least one bridge-constituting divalent radical with
• Carbonyl carbon atom of an amide group is connected, wherein the
• bridge-constitutive divalent radical having two carbon atoms as bridging atoms which in turn may be arbitrarily substituted, but the bridging atoms are preferably independently substituted with radicals selected from hydrogen, branched or unbranched aliphatics having not more than 6 carbon atoms, alkylcarboxylic acids having not more than 5 carbon atoms or substituted divalent aliphatic radicals having at least 3, but not more than 5 carbon atoms, which connect the two bridge atoms together.
• Composition additionally has at least one primary amine group.
• the molar ratio of the total number of primary and secondary amine groups to the number of tertiary amine groups is less than 5, preferably less than 4, but preferably greater than 0.75, more preferably greater than 1.
• compositions are preferred according to the invention, the abovementioned condition preferably being fulfilled for those compositions according to the invention for which at least one adhesion promoter according to component (C) is present, which contains both at least one primary amine group and at least one secondary amine group, wherein the secondary amine group is connected via at least one bridging divalent radical to the carbonyl carbon atom of an amide group, wherein the
• bridge-constitutive divalent radical having two carbon atoms as bridging atoms and in particular for such inventive compositions for which the proportion of the above-described adhesion promoter based on the component (C) at least 20 wt .-%, preferably at least 50 wt .-%, is.
• the molar ratio of the total number of primary and secondary amine groups to the total number of tertiary amine groups according to the invention is experimentally available from the difference of the total base number determined in potentiometric titration means
• the sample of the adhesion promoter (C) according to the present invention is ideally the substance or a concentrated one
• Dosage form of the coupling agent which should not be a water-based dosage form, or directly from the reaction mixture for the preparation of the same. Furthermore, it has been found that, according to the invention, those compositions are preferred in which the molecular weight of the adhesion promoter of component (C) is above 200 g / mol, preferably above 400 g / mol, more preferably above 500 g / mol.
• the property conferred thereon of the adhesion promoters to be immobilized in a sufficient amount on the conversion-treated metal surface may also be favored if the total of all adhesion promoters according to component (C) containing acidic aqueous composition has a weight-average molecular weight above 500 g / mol, preferably above 1, 000 g / mol. Such a totality is therefore preferred according to the invention.
• the weight-average molar mass becomes experimental over the size-exclusion chromatography with concentration-dependent refractive index detector at 30 ° C
• the sample is ideally the substance or a concentrated dosage form of the adhesion promoter, for example an aqueous concentrate thereof, or directly the
• Reaction mixture for the preparation of the bonding agent (C) refer.
• the evaluation of the molar mass averages follows the strip method with a calibration curve of the 3rd order.
• As a column material is hydroxylated polymethacrylate and as eluent an aqueous solution of 0.2 mol / L sodium chloride, 0.02 mol / L sodium hydroxide, 6.5 mmol / L ammonium hydroxide.
• the adhesion promoter according to component (C) to be used in the acidic aqueous composition can result from the reaction of a di- or polyamine with an ⁇ , ⁇ -unsaturated carboxylic acid and its ester and amide.
• the spontaneous and exothermic reaction proceeds via at least one aza-Michael addition of the diamine or polyamine to the ⁇ , ⁇ -unsaturated carboxylic acid or the ⁇ , ⁇ -unsaturated carboxylic acid ester or the ⁇ , ⁇ -unsaturated carboxylic acid amide.
• Higher molecular weight adhesion promoters according to component (C) are formed after amidation of the carboxylic acid, of the ester or of the amide with further diioder polyamines via subsequent aza-Michael additions.
• Composition preferably obtainable by one-pot reaction of an amount of one or more di- and / or polyamines, preferably one or more alkylenediamines with not more than 12 carbon atoms, more preferably not more than 6
• Preferred diamines for the one-pot reaction described above are 1,2-xylylenediamine, 1,3-xylylenediamine, 1,4-xylylenediamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, ethylenediamine, 1, 3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, 1,3-diaminobutane, 1,2-diaminobutane, 1,5-diaminopentane, 1,4-diaminopentane, 1,3-diaminopentane, 1, 2-diaminopentane, 1,6-diaminohexane, 1,5-diaminohexane, 1,4-diaminohexane, 1,3-diaminohexane, 1,2-di
• diamines according to the invention are amine-terminated polyethylene or
• Polypropylene oxides and amine-terminated copolymers of ethylene oxide and propylene oxide are each commercially available in the product series Jeffamine® D, Jeffamine® ED and Jeffamine® DER and Jeffamine® THF from Huntsmen.
• Preferred polyamines for the one-pot reaction described above are spermidine, spermine, dipropylenetriamine, diethylenetriamine, tripropylenetetramine, triethylenetetramine, tetraethylenepentamine, hexaethyleneheptamine, 1- (2-aminoethyl) -piperazine,
• polyamines according to the invention are amine-terminated polyethylene or
• Polypropylene oxides and amine-terminated copolymers of ethylene oxide and propylene oxide each commercially available in the product series Jeffamine® T and Jeffamine® THF from Huntsmen.
• the reaction mixture resulting from such a one-pot reaction can be added directly to an acidic aqueous composition containing components (A) and (B) to provide a composition of the invention.
• the one-pot reaction is preferably carried out "in substance", so that the proportion of components other than di- and polyamines and ⁇ , ⁇ -unsaturated carboxylic acids and their esters and amides preferably below 10 wt .-%, more preferably below
• component (C) of the composition according to the invention that the amount of di- and / or polyamines is initially introduced and the amount of ⁇ , ⁇ -unsaturated carboxylic acids, ⁇ , ⁇ -unsaturated carboxylic acid esters and / or ⁇ , ⁇ -unsaturated carboxylic acid amides is added in portions, while the
• Reaction temperature preferably 120 ° C, more preferably 100 ° C, especially preferably does not exceed 80 ° C.
• Reaction products advantageous in a subsequent condensation phase in which the reaction mixture for a predetermined period of first elevated temperature in the mass density system, for example, under reflux, is exposed and immediately followed by volatile condensation products by distillation from the
• Reaction mixture are at least partially removed, insofar as ⁇ , ⁇ -unsaturated
• Carboxylic esters are added as starting material in portions, preferably in an amount corresponding to at least 80% of the ester alcohols available in the reaction mixture.
• the distillation can in turn be followed by a phase of elevated temperature in the mass-dense system, with the completion of the condensation phase is completed.
• the portionwise addition of the starting material to the amount of di- and / or polyamine present to provide a coupling agent (C) is preferably followed by such a condensation phase in which a temperature above that of each previously
• prevailing reaction temperature is adjusted, but preferably not above 200 ° C, more preferably not above 180 ° C.
• the distillation can preferably also be carried out under reduced pressure.
• Carboxylic acid esters and / or ⁇ , ⁇ -unsaturated carboxylic acid amides is presented and the amount of di- and / or polyamines added in portions, is possible.
• the presentation of the amount of di- and / or polyamines for the formulation of inventive compositions is preferred.
• the adhesion promoters of component (C) for providing a composition of the invention upon presentation of the amount of the di- and / or polyamines are preferably obtainable by the molar ratio of the amounts of reactants combined in the one-pot reaction the di- and / or polyamines to ⁇ , ⁇ -unsaturated carboxylic acids and their esters and amides not greater than 2, preferably not greater than 1, 5, more preferably not greater than 1, 2, particularly preferably not greater than 1, 0 but preferably is not smaller than 0.5, more preferably not smaller than 0.6, particularly preferably not smaller than 0.7.
• composition of the invention are preferably at least 0.005 g / kg, more preferably at least 0.01 g / kg, particularly preferably at least 0.05 g / kg, but preferably less than 5 g / kg, particularly preferably less than 1 g / kg, more preferably less than 0.5 g / kg of organic compounds which are adhesion promoters according to component (C).
• Primer coating leads than that only a conversion of the metal surfaces in a small layer support ( ⁇ 1 ⁇ ) is realized.
• component (C) Of greater importance than the absolute amount of component (C) has its relative proportion based on the amount of components (A) contained, as this determines the balance between organic and inorganic content of the conversion layer. It has in this context as advantageous for the suppression of corrosive delamination of subsequently applied paint layers and the formation of homogeneous
• Conversion layers proven when the weight ratio of the component (A) calculated as Zr to the component (C) is not less than 0.2, preferably not less than 0.5, but preferably not greater than 10, more preferably not greater than 5. Corresponding acidic aqueous compositions are therefore preferred according to the invention.
• the acidic aqueous composition according to the invention can be further organic
• water-soluble or water-dispersible acrylates epoxides, urethanes or copolymers of olefins and ⁇ , ⁇ -unsaturated carboxylic acids or their esters, as well as copolymers of vinylphosphonic acid with unsaturated monomers, polyvinyl alcohols or polyalkyleneimines.
• the composition according to the invention contains
• (C) at least 0.005 g / kg, preferably at least 0.01 g / kg, more preferably at least 0.05 g / kg, but preferably less than 5 g / kg, more preferably less than 1 g / kg of coupling agents, each represent an organic compound having at least one tertiary amine group, each having a
• bridge-constituting divalent radical having the carbonyl carbon atom of an amide group, wherein the bridge-constituting divalent radical has two carbon atoms as bridging atoms, preferably obtainable by one-pot reaction of an amount of one or more di- and / or polyamines, preferably one or more alkylenediamines not more than 12
• (E) contains at least one water-soluble compound having a
• Standard reduction potential at pH 0 above +0.6 V SHE
• inorganic nitrogen compounds more preferably from nitric acid and / or nitrous acid and their salts
• (F) additionally an amount of zinc ions, preferably at least 0.1 g / kg of zinc ions;
• weight ratio of component (A) calculated as Zr to component (C) is not less than 0.2, preferably not less than 0.5, but preferably not greater than 10, more preferably not greater than 5, and
• the present invention relates to a method for
• Composition were painted, is painted.
• a metallic material according to the second aspect of the present invention consists of more than 50 at.% Of one or more metallic elements with a standard reduction potential Me ° - »Me n + + ne - of not more than +0.2 V (SHE) and not less than -2.4 V (SHE).
• metallic elements are the constituent elements of the material and preferably selected from Fe, Zn, Al, Mg, Sn or Ni.
• the metallic material may contain any other metallic or non-metallic elements.
• the metallic material can also be a metallically coated substrate, insofar as the metallic coating has a layer thickness of at least 1 ⁇ m and at least 50 at.% Consists of the constituent elements defined above.
• Such materials are all plated iron materials such as electrolytically or hot dip galvanized steel, preferably platings in the form of zinc (Z), aluminum-silicon (AS), zinc-magnesium (ZM), zinc-aluminum (ZA), aluminum-zinc (AZ). or zinc-iron (ZF).
• the components treated in accordance with the present invention can be any arbitrarily shaped and configured spatial structures which originate from a fabrication process, In particular, also semi-finished products such as strips, sheets, rods, tubes, etc., and composite structures assembled from the aforementioned semi-finished products, wherein the
• An iron material is characterized in that its content of iron is more than 50 at.%.
• Preferred ferrous materials are steel, the steel comprising metallic materials whose mass fraction of iron is greater than that of any other element, and whose carbon content, excluding carbides, is less than 2.06% by weight.
• the component consists either of ferrous materials or as composite construction with other metallic materials at least partially surfaces of the material iron, wherein preferably at least 5%, more preferably at least 10%, particularly preferably at least 20% of surfaces of the component formed by metallic materials in a composite construction are surfaces of the material iron, preferably of the material steel.
• step ii) it is preferable to apply an organic coating as a coating, especially a powder coating or dip coating, which again preferably an electrodeposition paint, more preferably a cathodic electrodeposition paint.
• the cathodic electrodeposition paint is based on an aqueous dispersion of an amine-modified film-forming polyepoxide, which preferably additionally comprises blocked and / or unblocked isocyanate-containing organic compounds as curing agents.
• the electrodeposition coating preferably follows a rinsing step, but particularly preferably no drying step.
• 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-based liquid medium contains no chemical components that cause a significant surface coverage of the components made of metallic materials with subgroup elements, semi-metal elements or polymeric organic compounds.
• a significant surface coverage is present when the liquid medium of the sink is depleted by at least 10 milligrams per square meter of the flushed surfaces, preferably by at least 1 milligram per square meter of the flushed surfaces, based on these components relative to the respective element or the respective polymeric organic compound without taking account of gains due to carryover and losses due to removal of wet films adhering to the component.
• a drying step is any method step in which the provision and use of technical means the drying of the aqueous, adhering to the surface of the component liquid film is intended and not merely caused by chance, in particular by supplying thermal energy or imposition of air flow.
• Material having its constituent element is zinc, for example galvanized steel, preferably that same containing surfaces with a thin amorphous layer Iron are applied, so that the surfaces of these materials as effective conversion layer formation in step i) of the method according to the invention is assigned, 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 US Pat
• WO 2008135478 A1 is described in each case as a wet-chemical process which can be used in an equivalent manner immediately before carrying out process step i) according to the invention.
• the component is at least partially composed of the material zinc, that the surfaces of the component, which are made of these materials, an iron occupancy of at least 20 mg / m 2 , but preferably not more than 150 mg / m 2 .
• the present invention relates to a painted metallic substrate having a mixed organic-inorganic intermediate layer consisting of oxides, hydroxides and / or oxyfluorides of the elements Zr, Ti and / or Si and organic
• An intermediate coating in the context of the third aspect of the present invention is when starting from the metallic substrate said intermediate layer is realized and immediately after the coating is applied.
• Preferred embodiments of the organic compounds in the context of the third aspect of the present invention having at least one tertiary amine group connected through a bridging divalent radical to the carbonyl carbon of an amide group, wherein the bridging divalent radical has two carbon atoms as bridging atoms are identical to those organic compounds which are preferred as adhesion promoters in the context of the first aspect of the present invention.
• the present invention relates to the use of a
• Adhesion promoter selected from organic compounds having at least one tertiary amine group, which has a bridge-constituting divalent radical with the Carbonyl carbon atom of an amide group is connected, wherein the
• bridge-constitutive divalent radical has two carbon atoms as bridging atoms, wherein the organic compounds have a weight average molecular weight above 500 g / mol, for the pretreatment of metal surfaces prior to painting.
• Preferred structural embodiments of the organic compounds which constitute a coupling agent in the context of the fourth aspect of the present invention are identical to those found preferred in the context of the first aspect of the present invention with respect to the coupling agent.
• Sheets of different metallic materials were cleaned, pretreated and electrocoated according to the following flow chart.
• G Cathodic electrodeposition coating (CathoGuard 800, BASF Coatings): Layer thickness of 20-22 ⁇ after drying in a baking oven at 180 ° C for
• the condensation phase was initiated by heating at a constant heating rate within half an hour to a temperature of the reaction mixture above 120 C, but only up to that
• the jacket temperature was maintained for a further 90 minutes under reflux conditions. During this time, the temperature of the reaction mixture dropped to about 90 C. Subsequently, the reflux conditions were abolished and changed to the distillation operation. For this purpose, the jacket temperature was increased stepwise to 165 ° C. while removing the methanol and kept at this maximum temperature for 30 minutes. The entire condensation phase lasted 285 minutes.
• the reaction mixture was then cooled to 100 ° C and added with vigorous stirring, such an amount of water ( ⁇ ⁇ Scm -1 ) that a 10 wt .-% aqueous concentrate of the respective adhesion promoter was obtained.
• Thread lengths in mm according to Daimler PAPP PWT 3002

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• 2017
  • 2017-08-08 EP EP17749456.4A patent/EP3504357A1/de active Pending
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