EP2094793A1 - Agent anticorrosion formant une couche de vernis à fissuration réduite, et procédé pour son application sans courant - Google Patents

Agent anticorrosion formant une couche de vernis à fissuration réduite, et procédé pour son application sans courant

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Publication number
EP2094793A1
EP2094793A1 EP07802356A EP07802356A EP2094793A1 EP 2094793 A1 EP2094793 A1 EP 2094793A1 EP 07802356 A EP07802356 A EP 07802356A EP 07802356 A EP07802356 A EP 07802356A EP 2094793 A1 EP2094793 A1 EP 2094793A1
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EP
European Patent Office
Prior art keywords
substrate
coating composition
composition according
acids
groups
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.)
Withdrawn
Application number
EP07802356A
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German (de)
English (en)
Inventor
Michael Dornbusch
Andrea Wiesmann
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.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
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Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP2094793A1 publication Critical patent/EP2094793A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/088—Autophoretic paints

Definitions

  • Methods and coating compositions for the current-free corrosion protection coating of various metal substrates are known. They offer in comparison to anodic or cathodic dip coating (ATL or KTL), in which the application of electrical voltages is necessary, in particular the advantage of simpler and cheaper process and the shorter process time. In particular, cavities in or edges on the substrates to be coated can be better coated with the electroless methods than with methods in which the application of electrical voltages is necessary.
  • electroless anticorrosion coating also called ACC process (Autophoretic Chemical Coating)
  • polymers for example emulsion polymers containing acrylates or styrene / butadiene, are used, which are anionically stabilized.
  • the ACC methods have the disadvantage that the deposited layers have defects that make the substrate significantly more susceptible to corrosion. Therefore, such deposited by ACC process layers are usually processed by rinsing with chromium-containing aqueous coating compositions to improve the corrosion protection at the defects.
  • chromium-containing coating agents have great problems with environmental compatibility and must be classified as highly hazardous to health.
  • ACC coating compositions containing salts of the lanthanide and the d elements and an organic film-forming component likewise ensure very good corrosion protection comparable to chromium-containing coating compositions.
  • a corrosion inhibitor is described which contains a vanadium component and a further component which contains at least one metal selected from zirconium, titanium, molybdenum, tungsten, manganese and cerium.
  • a disadvantage of corrosion protection agents according to WO-A-01/86016 is the tendency of the metal ions formed from the substrate to migrate through the deposited corrosion protection layer, since the polymers lead to a defective film formation.
  • a chromium-free aqueous corrosion inhibitor which contains as components hexafluoro anions of titanium (IV) and / or zirconium (IV), vanadium ions, transition metal ions and phosphoric and / or phosphonic acid.
  • a disadvantage of corrosion inhibitors according to WO-A-99/29927 is the tendency of the metal ions formed from the substrate to migrate through the deposited corrosion protection layer, since the polymers lead to poor film formation, and the use of ecologically critical substances, in particular hydrofluoric acid or fluorides.
  • WO-A-96/10461 describes an aqueous corrosion inhibitor containing as components anions having a central atom selected from the group titanium, zirconium, hafnium, silicon and at least 4 fluorine atoms as ligands and an organic polymer dispersion.
  • a disadvantage of the invention according to WO-A-96/10461 is that in the deposition of the anticorrosion agent on the substrate surface, the polymer dispersion particles flocculate and form a small contact surface with the surface. Furthermore, the latex particles have the disadvantage of having a lower migration rate in the diffusion in cavities or on edges of three-dimensional substrates in comparison to molecular dispersed polymers.
  • layers of a thickness between 1 micrometer and 1 mm are formed, which requires a corresponding material requirement per surface area. unit of the substrate to be coated. Layers with such thicknesses have a pronounced tendency to crack during drying, especially at high temperatures.
  • Another disadvantage is the tendency of the metal ions formed from the substrate to migrate through the deposited anticorrosion layer and the use of ecologically critical substances, in particular hydrofluoric acid or fluorides.
  • DE-A-37 27 382 comprises chromium-free aqueous dispersions of adducts of carboxylic acids and isocyanates with epoxides, which are suitable for the autophoretic coating of metallic surfaces.
  • Such dispersions have a particle diameter of less than 300, preferably between 100 and 250 nm in dispersed form and can be crosslinked after deposition on the metal surface at temperatures between 60 and 200 ° C.
  • latex particles have the disadvantage of having a lower migration rate in the diffusion in cavities or on edges of three-dimensional substrates in comparison to molecular dispersed polymers.
  • layers of a thickness between 1 micrometer and 1 mm are formed, which requires a corresponding material requirement per unit area of the substrate to be coated.
  • DE-A-103 30 413 describes coating compositions which are suitable for coating metallic surfaces and which may contain caprolactam-modified polyisocyanates based on polyethyleneimines.
  • the coating compositions can be applied by dip coating be applied and have after drying thicknesses between 1 and 300 microns. Sheets produced in this way also have a high material requirement and have a pronounced tendency to crack during drying, in particular at high temperatures.
  • the anticorrosive agent should substantially prevent the migration of the metal ions formed from the substrate and be deposited well on edges and in cavities of the substrate. Furthermore, the influence of foreign metal ions should be kept as low as possible and an effective corrosion protection can be achieved with comparatively low use of material. Furthermore, the conversion protection agent should develop effective protection for as many different metal substrates as possible and be largely independent of the redox potential of the substrate to be coated. In particular, the tendency for crack formation in the anticorrosion layer during drying and in the baking step should be suppressed since the anticorrosive effect is significantly impaired by the channels resulting from the cracking by the lacquer layer.
  • an aqueous coating composition which contains a water-dispersible and / or water-soluble polymer P and a surface-active substance OS on the surface of the substrate to be coated, the polymer P having statistically distributed covalently bound ligands A, which with the released in the corrosion of the substrate Metal ions and / or form chelates with the substrate surface, and having randomly distributed crosslinking functional groups B, which with itself, with further functional groups B 'of the polymer P and / or with other functional groups B and / or B' to crosslinkers V covalent Can form bonds.
  • an aqueous coating agent for metallic substrates with a good corrosion protection contains the aforementioned water-dispersible and / or water-soluble polymer P and a surface-active substance OS on the surface of the substrate to be coated, wherein the thickness of the coating after autodepositing between 5 and 900 nm.
  • the substrate is pretreated before deposition of the corrosion protection agent according to the invention in a further upstream process step with a corrosion inhibitor K.
  • the water-dispersible and / or water-soluble polymers P of the coating composition according to the invention carry ligands A, which form chelates with the metal ions released upon corrosion of the substrate, and crosslinking functional groups B which covalently bond to crosslinkers V with themselves and / or with further functional groups C. Can form bonds.
  • water-dispersible or water-soluble means that the polymers P in the aqueous phase aggregates with a form average particle diameter of ⁇ 50, preferably ⁇ 35 nm and particularly preferably ⁇ 20 nanometers or are solved molecular disperse.
  • aggregates differ significantly in their mean particle diameter from particles of dispersion, as described, for example, in DE-A-37 27 382 or WO-A-96/10461.
  • Molecular dispersions of dissolved polymers P generally have molecular weights of ⁇ 100,000, preferably ⁇ 50,000, more preferably ⁇ 10,000 dalton.
  • the size of the aggregates consisting of polymer P is accomplished in a conventional manner by introducing hydrophilic groups HG on the polymer P.
  • hydrophilic groups HG on the polymer P depends on the solvation capacity and the steric accessibility of the groups HG and can also be set by a person skilled in the art in a manner known per se.
  • Preferred hydrophilic groups HG on the polymer P are ionic groups, in particular sulfate, sulfonate, phosphate, phosphonate, ammonium and / or carboxylate groups, and nonionic groups, in particular hydroxyl, primary, secondary and / or tertiary Amine and / or amide groups, and / or oligo- or polyalkoxy substituents, such as preferably ethoxylated or propoxylated substituents, which may be etherified with further groups.
  • the hydrophilic groups HG may be identical to the ligands A and / or crosslinking groups B and B 'described below.
  • the polymer backbone of the polymers P can be any desired polymers, preferably those having molecular weights of 500 to 50,000 daltons, more preferably having molecular weights of 700 to 20,000 daltons.
  • the polymer backbone used are preferably polyolefins or poly (meth) acrylates, polyurethanes, polyalkylenimines, polyvinylamines, polyalkyleneamines, polyethers, polyesters and polyalcohols, which are in particular partially acetalized and / or partially esterified.
  • the polymers P can be linear, branched and / or be constructed dendritic.
  • Very particularly preferred polymer backbones are polyalkyleneimines, polyvinylamines, polyalcohols, poly (meth) acrylates and hyperbranched polymers, as described, for example, in WO-A-01/46296.
  • the polymers P are preferably stable to hydrolysis in the acidic pH range, in particular at pH values ⁇ 5, particularly preferably at pH values ⁇ 3.
  • Suitable ligands A are all groups or compounds which can form chelates with the metal ions released upon corrosion of the substrate. Preference is given to mono- and / or polydentate potentially anionic ligands. Particularly preferred ligands are
  • ureas and / or thioureas especially acylthioureas such as benzoylthiourea,
  • Oximes preferably 1,2-dioximes, such as functionalized diacetyldiols, organo-sulfur compounds, such as, in particular, optionally functionalized thiols, such as thioethanol, thiocarboxylic acids, thio aldehydes, thioketones, dithiocarbamates, sulfonamides, thioamides and, with particular preference, sulfonates,
  • 1,2-dioximes such as functionalized diacetyldiols, organo-sulfur compounds, such as, in particular, optionally functionalized thiols, such as thioethanol, thiocarboxylic acids, thio aldehydes, thioketones, dithiocarbamates, sulfonamides, thioamides and, with particular preference, sulfonates,
  • 1,2-dioximes such as functionalized diacetyldiols, organo-
  • Organophosphorus compounds in particular phosphates, more preferably phosphoric acid esters of (meth) acrylates, and also phosphonates, particularly preferably vinylphosphonic acid and hydroxy-, amino- and amido-functionalized phosphonates, optionally functionalized organoboron compounds, in particular boric acid esters,
  • optionally functionalized polyalcohols in particular carbohydrates and derivatives thereof, and chitosans, optionally functionalized acids, in particular di- and / or oligofunctional acids, or optionally functionalized (poly) carboxylic acids, in particular carboxylic acids, which are bonded to metal centers ionically and / or coordinately preferably (poly) methacrylates having acid groups or di- or oligofunctional acids,
  • heterocycles such as quinolines, pyrrolidines, in particular imin-functionalized pyridines, pyrimidines, pyrroles, furans, thiophenes, imidazoles, benzimidazoles, are preferred
  • Suitable crosslinking functional groups B on the polymer P are those which can form covalent bonds with themselves and / or with complementary functional groups B '.
  • the covalent bonds are preferably formed thermally and / or by the action of radiation. Particularly preferably, the covalent bonds are formed thermally.
  • the crosslinking functional groups B and B ' cause the formation of an intermolecular network between the molecules of the polymer P.
  • Under the action of radiation-crosslinking functional groups B and B' have activatable bonds, such as carbon-hydrogen, carbon-carbon, Carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon Single or double bonds. In this case, carbon-carbon double bonds are particularly advantageous.
  • Particularly suitable carbon-carbon double bonds as groups B are
  • Thermally crosslinking functional groups B can form covalent bonds with themselves or preferably with complementary crosslinking functional groups B 'under the influence of thermal energy.
  • thermal crosslinking functional groups B and B ' are particularly suitable thermal crosslinking functional groups B and B 'are
  • Azide groups acid groups, especially carboxylic acid groups,
  • Acid anhydride groups in particular carboxylic anhydride groups,
  • Acid ester groups in particular carboxylic acid ester groups,
  • Ether groups more preferably carbamate groups
  • isocyanate groups which are very particularly preferably reacted with blocking agents which deblockieren at the stoving temperatures of the coating compositions of the invention and / or are incorporated without deblocking in the forming network.
  • thermally crosslinking groups B and complementary groups B ' are particularly preferred:
  • crosslinkers V with groups B and / or B 'thermally and / or by radiation-crosslinking groups in principle all crosslinkers known to the person skilled in the art are suitable. Preference is given to low molecular weight or oligomeric crosslinkers V having a molecular weight of ⁇ 20,000 daltons, more preferably ⁇ 10,000 daltons.
  • the backbone of the crosslinker V carrying the crosslinking groups B and / or B ' can be linear, branched and / or hyperbranched. Preference is given to branched and / or hyperbranched structures, for example those as described in WO-A-01/46296.
  • the crosslinkers V are preferably stable to hydrolysis in the acidic pH range, in particular at pH values ⁇ 5, particularly preferably at pH values ⁇ 3.
  • crosslinkers V carry the above-described crosslinking groups B and / or B ', which react with the crosslinking groups of the polymer P with the formation of covalent bonds.
  • crosslinkers V with groups B and / or B 'thermally and optionally additionally crosslinked by the action of radiation.
  • the crosslinkers V carry in addition to the crosslinking groups B and / or B 'ligands L, which may be identical to and / or different from the ligands L of the polymer P.
  • Particularly suitable crosslinking functional groups B and B 'for the crosslinkers V are:
  • Acid anhydride groups in particular carboxylic anhydride groups,
  • Urea groups especially isocyanate groups, which are very particularly preferably reacted with blocking agents which deblock at the stoving temperatures of the novel coating compositions and / or are incorporated into the forming network without deblocking, (meth) acrylate groups,
  • Very particularly preferred crosslinkers V are branched and / or hyperbranched polyisocyanates which are at least partially blocked and which additionally carry ligands L.
  • the crosslinkers V carry groups B and / or B 'which are capable of forming covalent bonds with the ligands L of the polymer P.
  • the surface-active substance OS on the surface of the substrate to be coated contains at least one component KOS, which reduces the surface tension of the coating agent of the invention during autodeposition on the uncoated substrate surface and / or during the subsequent drying step.
  • the component KOS can be selected from the group of anionic, cationic and nonionic surfactants.
  • Amphiphilic substances which may be low molecular weight, oligomeric and / or polymeric, are preferably used.
  • low molecular weight is meant that the average molecular weights of the surface active component KOS are up to 2000 daltons, more preferably up to 1000 daltons, under "oligomer in that the surface-active component KOS has about 2 to 30, preferably 3 to 15, preferably repeating building blocks and has an average molecular weight between about 200 and 4000 daltons, preferably between about 500 and 3000 daltons, and under "polymer” that the surface-active component KOS has more than 10 preferably repeating building blocks and an average molecular weight of more than 500 daltons, preferably of more than 1000 daltons.
  • the surface-active components KOS are different from the polymer P according to the invention.
  • alkylcarboxylic acids and their salts alpha-omega-dicarboxylic acids and their salts, alpha-omega-dialcohols, alpha-omega-diamines and -amides and their salts, alkylsulfonic acids and their salts are preferred as low molecular weight substances and alkylphosphoric acids and alkylphosphonic acids and salts thereof.
  • Preferred oligomeric and / or polymeric surface-active substances are polyalkylene glycols, polyvinyl lactams, such as, for example, polyvinyl pyrrolidone and polyvinyl caprolactam, polyvinylimidazoles, polyvinyl alcohols and Polyvinylace- used.
  • Adhesive and / or 1, 6-hexanediol are very particularly preferred as surface-active component KOS as low-molecular substances and poly (oligo) ethylene glycols and / or poly (oligo) propylene glycols as oligomeric and / or polymeric substances.
  • the proportion of the surfactant OS on the inventive coating composition is preferably between 10 ⁇ 4 and 5 wt .-%, preferably between 10 "2 and 2 wt .-%, based on the coating composition, wherein the component KOS in the surfactant OS preferably in proportions of from 1 to 100% by weight, based on OS, more preferably in proportions of from 2 to 100% by weight.
  • water is used for the coating material according to the invention, preferably deionized and / or distilled water.
  • substantially water-miscible solvents in proportions of up to 30% by weight, preferably up to 25% by weight, based on the continuous phase, can be present in the continuous phase.
  • Preferred water-miscible solvents are ethanol, propanol, methyl ethyl ketone, N-ethyl pyrrolidone.
  • the water-miscible solvents are used in proportions of from 1 to 30% by weight, based on the continuous phase, preferably in amounts of from 2 to 25% by weight. used.
  • the pH of the coating composition according to the invention is preferably between 1 and 5, preferably between 2 and 4.
  • Particularly preferred acids are selected from the group of oxidizing mineral acids, in particular nitric acid, nitrous acid, sulfuric acid and / or sulphurous acid.
  • a buffer medium can be used, such as salts of strong bases and weak acids, in particular ammonium acetate.
  • the coating composition according to the invention additionally contains a salt which has as cationic constituent lanthanide metal cations and / or d-metal cations.
  • Preferred lanthanide metal cations are lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium and / or dysprosium cations. Very particular preference is given to lanthanum, cerium and praseodymium cations.
  • the lanthanide metal cations can be present in mono-, di- and / or trivalent oxidation state, the trivalent oxidation state being preferred.
  • Preferred d-metal cations are titanium, vanadium, manganese, yttrium, zirconium, niobium, molybdenum, tungsten, cobalt, ruthenium, rhodium, palladium, osmium and / or iridium cations.
  • Excluded as d-element cation is the chromium cation in all oxidation states.
  • Very particular preference is given to vanadium, manganese, tungsten, molybdenum and / or yttrium cations.
  • the d-element cations can be present in one to six valent oxidation state, with a three to six-valent oxidation state being preferred.
  • the substrate Prior to the application of the coating composition according to the invention, the substrate is purified in a preferred embodiment of the invention, in particular of oily and greasy residues, preferably detergents and / or alkaline cleaning agents being used.
  • a mechanical cleaning of the surface for example with grinding media, and / or a chemical removal of the surface layers, for example, with deoxidizing detergents done.
  • the thus pretreated substrate is brought into contact with the coating composition according to the invention. This is preferably done by immersing or pulling through the substrate in or by a bath containing the coating composition according to the invention.
  • the residence times of the substrate in the coating composition according to the invention are preferably 1 second to 15 minutes, preferably 10 seconds to 10 minutes and more preferably 30 seconds to 8 minutes.
  • the temperature of the bath containing the coating composition according to the invention is preferably between 20 and 90 ° C., preferably between 25 and 80 ° C., more preferably between 30 and 70 ° C.
  • the thickness of the layer produced with the coating composition according to the invention is preferably between 5 and 900 nm, particularly preferably between 10 and 800 nm, which, based on the anticorrosive effect, enables a significant saving in the material used.
  • the drying apparatus of the inventions for the beneficial effect can be regarded as largely uncritical. If the crosslinking groups B and / or B 'are at least partially radiation-curing, irradiation of the layer of the coating composition according to the invention, if appropriate in addition to the thermal treatment, is preferably carried out with actinic radiation and / or with electron radiation in a manner known to the person skilled in the art.
  • the coating composition according to the invention can be used on a wide range of substrates and is largely independent of the redox potential of the substrate.
  • Preferred substrate materials are zinc, iron, magnesium and aluminum, and their alloys, wherein the aforementioned metals are preferably present in the alloys to at least 20 wt .-%.
  • the substrates are formed as sheets, as used for example in the automotive industry, the construction industry and the mechanical engineering industry.
  • the coated with the coating material according to the invention sheets are used in particular in sheet metal as well as in coil coating (coil coating) of sheets used.
  • the coating compositions according to the invention are used for sealing cut edges of the sheets described above, in particular for sealing the cut edges of already coated sheets.
  • the substrates described above are coated prior to the deposition of the coating composition of the invention with a further electroless depositable corrosion inhibitor.
  • a further electroless depositable corrosion inhibitor Preference is given to anti-corrosion agents with inorganic constituents which have both a good adhesion to the layer of the coating composition according to the invention and to the uncoated substrate.
  • inorganic Corrosion inhibitors are described, for example, in EP-A-1 217 094, EP-AO 534 120, US-A-5,221, 371 and WO-A-01/86016.
  • an aqueous corrosion inhibitor K having a pH between 1 and 5 which at least one compound AA with a lanthanide metal as a cation and / or a d Contains elemental metal with the exception of chromium as cation and / or a d-element metalate with the exception of chromium-containing metalates as anion and BB at least oxidation-capable acid with the exception of phosphorus-containing and / or chromium-containing acids.
  • the salt forming the component AA has lanthanide metal cations and / or d-metal cations as its cationic constituent.
  • Preferred lanthanide metal cations are lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium and / or dysprosium cations. Very particular preference is given to lanthanum, cerium and praseodymium cations.
  • the lanthanide metal cations can be present in mono-, di- and / or trivalent oxidation state, the trivalent oxidation state being preferred.
  • Preferred d-metal cations are titanium, vanadium, manganese, yttrium, zirconium, niobium, molybdenum, tungsten, cobalt, ruthenium, rhodium, palladium, osmium and / or iridium cations.
  • Excluded as d-element cation is the chromium cation in all oxidation states.
  • Very particular preference is given to vanadium, manganese, tungsten, molybdenum and / or yttrium cations.
  • the d-element cations can be present in one to six valent oxidation state, with a three to six-valent oxidation state being preferred.
  • the concentration of the salt or salts (A) in the anticorrosion agent 10 is "1 to 10 " 4 mol / l, in particular 5 * 10 "1 to 10 " 3 mol / l.
  • the anions forming the salts AA with the d-element cations are preferably selected such that the abovementioned conditions for the solubility product LP are given.
  • Further preferred anions are halides, in particular chlorides and bromides.
  • the d-element cations can also be present as complexes with mono- and / or polydentate potentially anionic ligands.
  • Preferred ligands are optionally functionalized terpyridines and / or pyridines, in particular imin-functionalized pyridines, optionally functionalized pyrimidines, optionally functionalized benzimidazoles, optionally functionalized quinolines, optionally functionalized imidazoles, possibly functionalized thiazoles, optionally functionalized oxazoles, optionally functionalized pyrazoles, optionally functionalized Ureas and / or optionally substituted thioureas, optionally functionalized amines and / or polyamines, in particular EDTA, imines, in particular imin-functionalized pyridines, organosulfur compounds, in particular optionally functionalized thiols, thiocarboxylic acids, thioaldehydes, thioketones, dithiocarbamates
  • the salts contain AA d-element metalates as anions, which together with the d-element cations or alone can form the salt AA.
  • Preferred d-elements for the metallates are vanadium, manganese, zirconium, nickel, molybdenum and / or tungsten. Very particular preference is given to vanadium, manganese, tungsten and / or molybdenum. Excluded as d-element metalate are chromates in all oxidation states.
  • Particularly preferred d-element metallates are oxoanions, in particular tungstates, permanganates, vanadates and / or molybdates.
  • the preferred solubility product LP of such salts is the same as stated above.
  • Preferred cations of such salts are ammonium ions which are optionally substituted by organic radicals, phosphonium ions and / or sulfonium ions, alkali metal cations, in particular lithium, sodium and / or potassium, alkaline earth metal cations, in particular magnesium and / or calcium.
  • Particularly preferred are those with or without ganic radicals substituted ammonium ions and the alkali metal cations, which ensure a particularly high solubility product LP of the salt AA.
  • At least one acid capable of oxidation is used in such a way that the pH of the corrosion protection agent is between 1 and 5, preferably between 2 and 4.
  • Preferred acids BB are selected from the group of oxidizing mineral acids, in particular nitric acid, salicific acid, sulfuric acid and / or sulfurous acid.
  • a buffer medium such as salts of strong bases and weak acids, in particular ammonium acetate.
  • water is used for the coating material according to the invention, preferably deionized and / or distilled water.
  • the substrate Before the application of the anticorrosion agent K, the substrate is purified in a preferred embodiment of the invention, in particular of oily and greasy residues, preference being given to using detergents and / or alkaline cleaning agents.
  • the cleaning with detergents and / or alkaline cleaning agents is rinsed again with water before the application of the corrosion protection agent K after cleaning.
  • a mechanical cleaning of the surface for example with grinding media, and / or a chemical removal of the surface layers, for example with deoxidizing detergents.
  • the thus pretreated substrate is brought into contact with the anticorrosion agent K. This is preferably done by immersing or pulling through the substrate in or by a bath containing the corrosion inhibitor K.
  • the residence times of the substrate in the anticorrosion agent K are preferably 1 second to 10 minutes, preferably 10 seconds to 8 minutes and more preferably 30 seconds to 6 minutes.
  • the temperature of the bath containing the corrosion inhibitor K is preferably between 25 and 90 ° C., preferably between 30 and 80 ° C., more preferably between 35 and 70 ° C.
  • drying of the composite of substrate and anticorrosive agent is preferably carried out by dry blowing or by drying at temperatures between about 30 and 200 ° C., the drying temperature and the type or apparatus of drying having the advantageous effect of the corrosion inhibitor K can be regarded as largely uncritical.
  • the substrates coated with the corrosion protection agent K are coated with the coating composition of the invention. This is preferably done by immersing or pulling through the coated substrate or by a bath containing the coating composition according to the invention.
  • the residence times of the substrate in the coating composition according to the invention are preferably 1 second to 15 minutes, preferably 10 seconds to 10 minutes and more preferably 30 seconds to 8 minutes.
  • the temperature of the bath containing the coating composition according to the invention is preferably between 20 and 90 ° C., preferably between 25 and 80 ° C., more preferably between 30 and 70 ° C.
  • the thickness of the layer produced with the coating composition according to the invention is preferably between 5 and 900 nm, particularly preferably between 10 and 800 nm, which, based on the anticorrosive effect, enables a significant saving in the material used.
  • the Drying apparatus for the advantageous effect of the coating composition of the invention can be considered largely uncritical. If the crosslinking groups B and / or B 'are at least partially radiation-curing, irradiation of the layer of the coating composition according to the invention, if appropriate in addition to the thermal treatment, is preferably carried out with actinic radiation and / or with electron radiation in a manner known to those skilled in the art.
  • Example 1 b Preparation of the first basin with the corrosion inhibitor K2
  • counter-buffered to adjust the aforementioned pH with nitric acid solution In Comparative Example 1 b ', the above formulation without the surface-active substance Disperbyk 184 was used.
  • Example 3a Preparation of the Second Basin with the Coating Composition
  • it is counter-buffered to adjust the aforementioned pH with aqueous ammonia solution.
  • Example 3b Preparation of the second basin with the coating composition of the invention
  • Comparative Examples 3a 'and 3b' Preparation of the second basin with a coating agent according to Examples 3a and 3b without surface-active substance OS.
  • Example 4a Coating of the Substrate with the Corrosion Inhibitor K and the Coating Composition of the Invention
  • the substrate (made of galvanized steel plate) is cleaned for 5 minutes at 55 0 C in a cleaning solution (Ridoline C72 from. Henkel) and then rinsed with distilled water.
  • a cleaning solution Lidoline C72 from. Henkel
  • the rinsed with distilled water plate immediately immersed at 45 0 C for 4 minutes in the first basin of the corrosion inhibitor K1 according to Example 1a.
  • the coated sheet is rinsed with distilled water and blown dry with nitrogen.
  • the sheets are immersed for 5 minutes at 35 ° C. in the second basin of the anticorrosive agent according to the invention according to Example 3b. It forms an invisible to opalescent layer in the ⁇ / 4 range of visible light.
  • the coated sheet is rinsed with distilled water and blown dry with nitrogen.
  • the sheet is then dried for 20 minutes at 80 0 C.
  • Example 4b Coating of the Substrate with the Corrosion Inhibitor K and the Coating Composition According to the Invention
  • the substrate galvanized steel sheet
  • a cleaning solution Rholine C72 from Henkel
  • the rinsed with distilled water plate immediately at 45 ° C for 4 minutes in the first basin of the corrosion inhibitor K2 according to Example 1 b dipped.
  • the coated sheet is rinsed with distilled water and blown dry with nitrogen.
  • the sheets are immersed for 5 minutes at 35 ° C. in the second basin of the corrosion protection agent according to the invention according to Example 3a.
  • An invisible to opalescent layer forms in the ⁇ / 4 range of visible light.
  • the coated sheet is rinsed with distilled water and blown dry with nitrogen. The sheet is then dried for 20 minutes at 8O 0 C.
  • Comparative Example 4a Coating of the Substrate with the Corrosion Inhibitor K and the Coating Composition (without Surfactant OS)
  • the substrate (sheet of galvanized steel) is cleaned for 5 minutes at 55 ° C in a cleaning solution (Ridoline C72 Fa. Henkel) and then rinsed with distilled water. Subsequently, the rinsed with distilled water plate immediately at 45 0 C for 4 minutes in the first basin of the corrosion inhibitor K1 according to Example 1a 'immersed (without surfactant OS). Thereafter, the coated sheet is rinsed with distilled water and blown dry with nitrogen. Immediately thereafter, the sheets are immersed for 5 minutes at 35 ° C. in the second basin of the corrosion protection composition according to the invention according to Example 3b '(without surface-active substance OS). It forms an invisible to opalescent layer in the ⁇ / 4 range of visible light. Thereafter, the coated sheet is rinsed with distilled water and blown dry with nitrogen. The sheet is then dried for 20 minutes at 80 0 C.
  • a cleaning solution Radoline C72 Fa. Henkel
  • Comparative Example 4b ' Coating of the substrate with the anticorrosive agent K and the coating agent (without surface-active substance OS)
  • the substrate galvanized steel sheet
  • a cleaning solution Lidoline C72 from Henkel
  • the rinsed with distilled water plate immediately at 45 0 C for 4 minutes in the first basin of the corrosion inhibitor K2 according to Example 1 b 'immersed (without surfactant OS).
  • the coated sheet is rinsed with distilled water and blown dry with nitrogen.
  • the sheets are immersed for 5 minutes at 35 ° C. in the second basin of the corrosion protection composition according to the invention according to Example 3a '(without surface-active substance OS). It forms an invisible to opalescent layer in the ⁇ / 4 range of visible light.
  • the coated sheet is rinsed with distilled water and blown dry with nitrogen. The sheet is then dried for 20 minutes at 8O 0 C.
  • Example 5 Rapid corrosion test with Harrison solution on the measured Example 4 coated substrates
  • a Harrison solution (5g NaCl + 35g (NH 4 ⁇ SO 4 ) in 1000ml of demineralised water can be used as substrate for this purpose steel, galvanized steel or zinc alloys) on the samples coated with the above mentioned layer (6 * 6 cm ) a plastic cylinder with a diameter of 48 mm and a height of 6 cm is glued to the surface with an adhesive: Scrintec 600 silicone adhesive transparent, RTV 1 k oxime system (Ralicks, 46459 Rees) ml of Harrison solution These samples are subjected to an electrochemical impedance measurement (EIS) in a 2-electrode arrangement from 1 MHz to 10OmHz with an amplitude of 1 mV and open potential with a platinum network as counterelectrode.
  • EIS electrochemical impedance measurement
  • the thus prepared samples are subjected to weathering for a total of 20 cycles in a temperature range from 25 0 C to 73 ° C so that in each case the maxi- mum and is run through the minimum temperature within one hour.
  • the now dry cylinder is again filled with 30 ml Harrison solution, after 10 minutes residence time this solution is used to determine the possibly dissolved during the weathering ions by means of ICP-OES (Inductively Coupled Plasma - Optical Emission Spectrometry).
  • ICP-OES Inductively Coupled Plasma - Optical Emission Spectrometry
  • 70 ml of Harrison solution is added to the cylinder and a new EIS measurement is carried out.
  • a renewed weathering performed by the rapid test and then again taken an ICP-OES sample and made a further E IS measurement.
  • the measurement is verified by a double determination.
  • the ICP-OES data are normalized to the area of the samples. These data give a linear progression. Due to the linearity of the corrosion kinetics, the different coatings can be compared by the slopes of the graph.
  • the ICP-OES data represent the resolution of the substrate per area and time and are therefore a direct measure of the corrosion rate that is possible with a particular coating.
  • the EIS measurements are interpreted with regard to the formation of pores or other time constants in the spectrum. In addition to the observation of the layer, it is also possible to characterize the paint in its properties more closely
  • Granodine 958 54 (Phosphation of Henkel) 17,7

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

L'invention concerne un produit de revêtement aqueux pour des substrats métalliques, contenant un polymérisat P dispersable dans l'eau et/ou soluble dans l'eau avec des ligands A liés par covalence, qui forment des chélates avec les ions métalliques libérés lors de la corrosion du substrat et/ou avec la surface du substrat, et avec des groupes fonctionnels coréticulés B1 qui peuvent former des liaisons covalentes sur des réticuleurs V avec eux-mêmes, avec d'autres groupes fonctionnels complémentaires B' du polymérisat P et/ou avec d'autres groupes fonctionnels B et/ou B', et contenant au moins une substance OS active en surface sur la surface du substrat à revêtir.
EP07802356A 2006-11-13 2007-09-19 Agent anticorrosion formant une couche de vernis à fissuration réduite, et procédé pour son application sans courant Withdrawn EP2094793A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006053292A DE102006053292A1 (de) 2006-11-13 2006-11-13 Lackschichtbildendes Korrosionsschutzmittel mit verminderter Rißbildung und Verfahren zu dessen stromfreier Applikation
PCT/EP2007/008136 WO2008058587A1 (fr) 2006-11-13 2007-09-19 Agent anticorrosion formant une couche de vernis à fissuration réduite, et procédé pour son application sans courant

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EP2094793A1 true EP2094793A1 (fr) 2009-09-02

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US (1) US20100065157A1 (fr)
EP (1) EP2094793A1 (fr)
JP (1) JP2010509503A (fr)
CN (1) CN101553541A (fr)
AR (1) AR063784A1 (fr)
DE (1) DE102006053292A1 (fr)
WO (1) WO2008058587A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE102009007633B4 (de) 2009-02-05 2013-09-26 Basf Coatings Ag Mehrstufiges Verfahren zur Lackierung metallischer Substrate
DE102009007632A1 (de) 2009-02-05 2010-08-12 Basf Coatings Ag Beschichtungsmittel für korrosionsstabile Lackierungen
DE102009007624A1 (de) * 2009-02-05 2010-08-12 Basf Coatings Ag Beschichtungsmittel für korrosionsstabile Lackierungen
JP6168992B2 (ja) * 2010-09-13 2017-07-26 ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツングＣｈｅｍｅｔａｌｌ ＧｍｂＨ 表面コーティング法および前記方法でコーティングした物体の使用
RU2013119809A (ru) * 2010-10-05 2014-11-20 Басф Се Способ пассивирования металлической поверхности
WO2015070933A1 (fr) 2013-11-18 2015-05-21 Basf Coatings Gmbh Procédé permettant de revêtir des substrats métalliques d'une couche de conversion et d'une couche sol-gel
US10934438B2 (en) * 2017-04-27 2021-03-02 Axalta Coating Systems Ip Co., Llc Coatings and methods for using and producing the same
DE102019100123B4 (de) 2019-01-04 2021-02-04 Excor Korrosionsforschung Gmbh Zusammensetzungen und Verfahren zur Vorbehandlung von Substraten für die nachfolgende Fixierung von Dampfphasen-Korrosionsinhibitoren

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US6989411B2 (en) * 2001-11-14 2006-01-24 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Epoxy dispersions for use in coatings
US6727314B2 (en) * 2001-12-13 2004-04-27 Basf Ag Crosslinking systems for acrylic latex films
US20030134973A1 (en) * 2002-01-15 2003-07-17 Chen Robert Gow-Sheng Waterborne latexes for anti-corrosive and solvent-resistant coating compositions
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GB0307246D0 (en) * 2003-03-28 2003-04-30 Avecia Bv Aqueous pigmented coating composition with improved open-time comprising crosslinkable oligomer(s) and dispersed polymer(s)
DE10330413A1 (de) * 2003-07-04 2005-01-20 Basf Ag Caprolactam-blockierte Isocyanate sowie deren Verwendung zur Beschichtung von Oberflächen
DE10349728A1 (de) * 2003-10-23 2005-05-25 Basf Ag Im wesentlichen Chrom-freies Verfahren zum Passivieren von metallischen Oberflächen aus Zn, Zn-Legierungen, AI oder AI-Legierungen

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Also Published As

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AR063784A1 (es) 2009-02-18
JP2010509503A (ja) 2010-03-25
DE102006053292A1 (de) 2008-05-15
US20100065157A1 (en) 2010-03-18
CN101553541A (zh) 2009-10-07
WO2008058587A1 (fr) 2008-05-22

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