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EP0948666B2 - Procede de traitement de surfaces metalliques - Google Patents

Procede de traitement de surfaces metalliques Download PDF

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Publication number
EP0948666B2
EP0948666B2 EP97954820A EP97954820A EP0948666B2 EP 0948666 B2 EP0948666 B2 EP 0948666B2 EP 97954820 A EP97954820 A EP 97954820A EP 97954820 A EP97954820 A EP 97954820A EP 0948666 B2 EP0948666 B2 EP 0948666B2
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EP
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Prior art keywords
aqueous solution
acid
process according
group
atoms
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German (de)
English (en)
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EP0948666B1 (fr
EP0948666A1 (fr
Inventor
Hans-Jürgen P. ADLER
Christian Bram
Ralf Feser
Evelin JÄHNE
Christian Jung
Iris MÄGE
Jürgen Rudolph
Lars Sebralla
Martin Stratmann
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Chemetall GmbH
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Chemetall GmbH
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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
    • C23C22/07—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
    • 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
    • C23C22/68—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 solutions with pH between 6 and 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/58—Treatment of other metallic material
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/66—Treatment of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated

Definitions

  • the invention relates to a process for the treatment of metallic surfaces consisting of zinc, magnesium or aluminum or of the alloys of zinc, magnesium or aluminum and to which after the treatment lacquers, plastic layers, paints, sealants or adhesives are applied ,
  • scale surfaces are coated with an inorganic conversion layer (e.g., zinc phosphate) prior to the application of a lacquer or plastic layer.
  • an inorganic conversion layer e.g., zinc phosphate
  • conversion treatment by means of layer-forming phosphating or chromating the metallic surface is passivated and prepared for the usually subsequent coating with a paint or with a plastic.
  • the conversion treatment of aluminum surfaces is still carried out today by yellow chromating, using an acidic chromate solution with a pH of 1 to 2, which forms a protective layer on the aluminum.
  • the protective layer consists of an insoluble Aluminum-chromium (III) mixed oxide and causes the high passivity of the surface against corrosion.
  • the residual content of unused chromate ions deposited in the oxide layer additionally causes a self-healing effect in the case of a damaged coating of lacquer or plastic.
  • the yellow chromated aluminum surfaces has the disadvantage that it has only insufficient adhesion-promoting properties with respect to a paint and plastic layer.
  • chromate ions are washed out of free-weathered layers disadvantageously.
  • the DE-A 31 37 525 discloses a process for inhibiting corrosion in an aqueous system, wherein the aqueous system contains at least one water-soluble inorganic nitrite and at least one organic diphosphonic acid or at least one salt of the diphosphonic acid.
  • the diphosphonic acid is present in the aqueous system at a concentration of 0.1 to 20 ppm.
  • corrosion problems in cooling systems should be avoided.
  • especially the hydroxyethylidenediphosphonic acid and its inorganic salts are preferred.
  • benzimidazolyl-2-alkane-phosphonic acids and their salts have a pronounced corrosion-inhibiting effect and can be used as corrosion inhibitors.
  • They can be used individually, with each other or together with other known corrosion inhibitors.
  • the compounds are added for corrosion inhibition in general aqueous, aqueous-alcoholic, alcoholic and / or oil-containing media.
  • they can be used as corrosion inhibitors in heat carriers of cooling or heating circuits, cooling lubricants, mineral oils or Sparbeizen. the corrosion of metals is prevented by addition of the compounds and / or their salts to the media or circulatory liquids, in particular of copper and its alloys.
  • the benzimidazolyl-2-alkane-phosphonic acids contain a phosphonic acid group, a straight-chain or branched, saturated or unsaturated, bivalent, optionally substituted hydrocarbon radical having 1 to 15 carbon atoms and a substituted benzimidazole radical, where the straight-chain or branched hydrocarbon radical and the benzimidazole radical are in position 2 the benzimidazole radical are linked together.
  • DE-AS 1 013 814 teaches one-component reaction primer solutions (one-component "wash primer") for improving the printability of aluminum foils which contain not only hydroxyl-containing acetalized synthetic resin but also one or two oxygen-containing inorganic acids in hydroxyl-containing solvents and from 0.1 to 5% of an additive of organic hydroxyl group-containing acids or esters such as of oxybutyric acid or tartaric acid.
  • a method in which firstly a layer of aluminum is produced on an aluminum substrate at a pH value of from 2 to 14 and in which then at the Aluminum hydroxide layer is deposited by treatment with an organic phosphinic acid or an organic phosphonic acid another layer.
  • the organic radical of the phosphinic and phosphonic acid contains in each case 1 to 10 organic groups and 1 to 30 C atoms.
  • the molecule of the organic phosphinic and phosphonic acids contains from 1 to 10 phosphine and phosphonic acid groups.
  • an aqueous solution is used in which amines, amine alcohols, alkali hydroxides, alkaline earth hydroxides, alkali metal carbonates. Alkali bicarbonates or ammonia are included.
  • a solution is used in which the phosphinic and phosphonic acids are present in a concentration of 0.001 mol / l up to the saturation concentration and contains as solvent water, an alcohol or an organic solvent.
  • the phosphinic and phosphonic acids contain as organic groups, for example, aliphatic hydrocarbons, aromatic hydrocarbons, organic acids, aldehydes, ketones, amines, amides, thioamides, imides, lactams, anilines, piperidines, pyridines, carbohydrates, esters, lactones, ethers, alkenes, alcohols , Nitriles, oximes, silicones, ureas, thioureas, perfluorinated organic groups, silanes, and combinations of these groups.
  • the second layer should act on the substrate in particular as a good adhesion promoter for paint and plastic coatings and for paints.
  • the invention has for its object to provide a method according to which metallic surfaces, which consist of zinc, magnesium or aluminum or of the alloys of zinc, magnesium or aluminum, treated to the metallic surfaces in particular a good adhesion for Paints, plastic layers, paints, sealants and adhesives and to protect the metallic surfaces against corrosion.
  • the object underlying the invention is achieved in that the metallic surfaces are treated at 10 to 100 ° C by dipping, spraying or rolling with an aqueous solution having a pH of 2 to 13 and 10 -5 to 1 mol / l one or more compounds.
  • Y is a straight-chain alkyl group having 10 to 20 C atoms
  • X is a COOH, HSO 3 , HSO 4 , (OH) 2 PO, (OH) 2 PO 2 - , (OH) (OR ') PO or (OH) (OR') PO 2 - group
  • R ' is an alkyl group having 1 to
  • the effect of the method according to the invention is based on the ability of the compounds XYZ to spontaneously organize and to form very thin, closed films on metallic surfaces, in particular an orientation of the acidic groups in the direction of the metallic surface and between the hydroxyl groups on the metallic surface and the acidic groups of the compound XYZ is a chemical bond is formed.
  • the structure of the compounds XYZ was chosen according to the invention so that both a reactive binding of the thin film to the metal surface and to the matrix of paints, plastic coatings, paints, sealants and adhesives results.
  • the straight-chain organic group Y acts as a "spacer" between the groups X and Z; it virtually gives the compound XYZ the properties of a surfactant, since the organic group Y has hydrophobic properties.
  • the Z group imparts wettability and reactivity to the coated surface to paints, plastic coatings, paints, sealants and adhesives.
  • paints, plastic coatings, paints, sealants and adhesives are applied to the thin films, the advantageous properties of the thin films are retained even under the action of corrosive media, so that the metallic surfaces are protected against corrosion.
  • the reactive group Z should be matched in particular to the individual coatings.
  • aqueous solution 0.1 to 50% of the water is replaced by an alcohol having 1 to 4 carbon atoms, by acetone, by dioxane or by tetrahydrofuran.
  • organic solvents cause a higher solubility of the compounds XYZ, which are usually larger molecules whose solubility in pure water is not very high.
  • the solution always contains a large amount of water, so that even in the presence of organic solvents can still be spoken of an aqueous system.
  • the aqueous solution contains one or more compounds of the type XYZ in a concentration which is in the range of the critical micelle concentration.
  • the critical micelle formation concentration cmc is a characteristic of the particular surfactant concentration, in which the aggregation of the surfactant molecules to micelles begins. The aggregation is reversible. Below the cmc, ie, when the solutions are diluted, the micelles again break down into monomeric surfactant molecules.
  • the numerical value of cmc for each surfactant depends on its constitution as well as external parameters such as ionic strength, temperature and concentration of additives. Surface tension measurements are suitable as methods for determining the cmc.
  • the surface tension is determined ⁇ of a surfactant solution as a function of its concentration c at constant temperature by means of the ring or plate method.
  • the aqueous solution contains a defoamer and / or a solubilizer in each case in an amount of 0.05 to 5 wt .-%.
  • the defoamer facilitates the handling of the solution according to the invention, which tends to foam due to the surfactant properties of the compounds XYZ.
  • the solubilizer advantageously limits the use of organic solvents and favors the use of pure water. Both as defoamers and as solubilizers, for example, amino alcohols can be used.
  • the compounds of the type XYZ are present in the aqueous solution as salts.
  • the salts are generally more soluble than the compounds themselves, and moreover the dissolved salts are very stable, so that the handling of the solution according to the invention is improved by the use of the salts of the compounds XYZ.
  • the sodium and potassium salts are used.
  • Y is a straight-chain, straight-chain alkyl group having 10 to 12 C atoms. These groups Y give the compounds XYZ according to the invention very good adhesion-promoting properties for coatings and other organic coatings.
  • Aqueous solutions containing the following compounds of the type XYZ have very good adhesion-promoting and corrosion-inhibiting properties: 1-phosphonic acid 12-mercaptododecane, 1-phosphonic acid 12- (N-ethylamino) dodecane, 1-phosphonic acid 12-dodecene, 1,10-decanediphosphonic acid, 1,12-dodecanediphosphonic acid, 1-phosphoric acid 12-hydroxvdodecane, 1-phosphoric acid 12 (N-ethylamino) dodecane, 1-phosphoric acid 12-mercaptododecane, 1,10-decanediphosphoric acid, 1,12- Dodecanediphosphoric acid, 1-phosphoric acid 12-acryloyldodecane.
  • These compounds bond to the metallic surfaces via the phosphonic and phosphoric acid groups and act as adhesion promoters to the various organic constituents of the coatings, the plastic coatings, the paints, the sealants, both through their aliphatic group and through their functional group Z. and the adhesives.
  • the aqueous solution is applied by the known dipping, spraying or rolling at 10 to 100 ° C on the metallic surfaces, the dipping time 5 seconds to 20 minutes, the injection time 5 seconds to 15 Minutes and the rolling time is 2 to 120 seconds. It has been found that a thin film is formed on the metallic surfaces when the aqueous solution is applied by dipping, spraying or rolling, wherein rinsing of the treated metallic surfaces is not essential, but may be advantageous.
  • the metallic surfaces are stained alkaline and / or acid before applying the aqueous solution and then rinsed with water.
  • the used water can be desalted or not desalted.
  • the metallic surfaces consisting of zinc, magnesium, aluminum and their alloys are always covered by oxide layers and additionally contaminated by the superficial adsorption of carbon dioxide, water and / or hydrocarbons. These contaminated coatings are unable to permanently bond paints, plastic coatings, paints, sealants and adhesives and provide long term corrosion protection. Therefore, the metallic surfaces are cleaned in the manner according to the invention prior to treatment with the aqueous solution.
  • the metallic surfaces on which the aqueous solution was applied by dipping or spraying, then rinsed with water and optionally dried in a stream of nitrogen or air, wherein the temperature of the nitrogen or air flow is 15 to 150 ° C. Rinsing and drying does not hinder the formation of the thin film on the metallic surfaces.
  • the water used for rinsing may be desalted or not desalted.
  • the method according to the invention is used for the treatment of metallic surfaces, to which a cathodic or anodic electrodeposition paint, a powder coating, a coil coating lacquer, a low-solvent high-solids lacquer or a water-diluted lacquer is subsequently applied ,
  • a cathodic or anodic electrodeposition paint a powder coating, a coil coating lacquer, a low-solvent high-solids lacquer or a water-diluted lacquer is subsequently applied
  • the pretreatment of the metallic surfaces with the aqueous solution according to the invention has proven particularly useful.
  • the substrate sheets consist of the alloy AlMg1.
  • the sheets are immersed in an alkaline pickling solution containing 32 g / l NaOH and 8 g / l Na 2 CO 3 at room temperature for 3 minutes. Then it is rinsed with deionized water. Thereafter, the alkaline pickled sheets are immersed for 3 minutes at 40 ° C in an acid pickling solution containing 10 g / l H 2 SO 4 and 33 g / l H 2 O 2 . Then it is rinsed with deionized water. Finally, the pickled sheets are immersed in the aqueous solution according to the invention at 40 ° C. for 3 minutes, which contains the compound XYZ according to the invention in a concentration of about 10 -3 mol / l. This is followed by rinsing with demineralized water and drying at room temperature in a stream of nitrogen.
  • the sheets are first sprayed at 65 ° C for 10 seconds with an alkaline pickling solution containing 10 g / l Bonder V338M®. Subsequently, the sheets are rinsed by spraying with water. Thereafter, the alkaline pickled sheets are sprayed at 50 ° C for 30 seconds with an acidic pickling solution containing 16 g / l Bonder V450M®. Subsequently, the pickled sheets are rinsed by spraying with demineralized water. Finally, the sheets are sprayed with the aqueous solution according to the invention at 40 ° C for 30 seconds. This is followed by rinsing with deionized water and drying in a stream of air at room temperature.
  • the compound XYZ according to the invention is present in the aqueous solution in a concentration of about 10 -3 mol / l (® registered trademark of Metallgesellschaft AG, Frankfurt / Main, DE).
  • the sheets are pickled according to the spraying alkaline and acidic and rinsed. Subsequently, the aqueous solution according to the invention is rolled onto the sheets for two seconds at room temperature, wherein the roller is driven at 25 U / minute.
  • the compound XYZ is present in a concentration of about 10 -3 mol / l. After rolling the aqueous solution, the sheets are dried in a convection oven at 105 ° C.
  • the treated with the inventive aqueous solution panels were painted according to different methods. Both a cathodic electrodeposition paint and a powder coating as well as a polyester paint were used.
  • the electrocoating was electrolytically deposited on the sheets at a voltage of about 250 volts and then dried at 180 ° C for 22 minutes.
  • the powder coating was applied to the panels by electrostatic spraying and then dried at 200 ° C for 10 minutes.
  • the polyester coating system consisted of a primer and a topcoat. Both components were applied to the sheets by knife coating. The primer had a layer thickness of 5 microns, while the topcoat had a layer thickness of 25 microns. The stoving temperatures were 216 ° C for the primer and 241 ° C for the top coat.
  • the following table contains the test results which were measured when using different substances according to the invention.
  • the substances were present in the solutions according to the invention in a concentration of about 10 -3 mol / l.
  • the acetic acid-enhanced salt spray test ESS shows that the thin films produced according to the invention provide very good undercounter protection over the comparison sheets; Of the comparison sheets only the chromated sheet is sufficiently protected against corrosion.
  • the T-bend test which was carried out under the T 0 condition, as well as the cross-hatching with Erichsentiefung show that the paint adhesion is better on the inventively treated sheets than on the comparison sheets. Overall, therefore, the results obtained with the invention are surprisingly good, since they are equivalent to the result obtained with the chromating equivalent corrosion resistance and with respect to the paint adhesion significantly.
  • angle-dependent X-ray photoelectron spectroscopy By angle-dependent X-ray photoelectron spectroscopy (ARXPS) the orientation of the molecules of the compounds of the type XYZ was determined. Due to the very limited penetration depth of the characteristic photoelectrons, angle-resolved x-ray photoelectrospectroscopy allows a different information depth of the spectral data as a function of the angle ⁇ . Thus, the information depth at small angles in the range of about 1 nm and at larger angles in the range to about 10 nm. This allows to determine the orientation of the molecules. This method is, for example, in the publication of Briggs, Practical Surface Analysis, 1990, Wiley & Sons, Chichester , described. FIG.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • ing And Chemical Polishing (AREA)
  • Paints Or Removers (AREA)

Claims (12)

  1. Procédé de traitement de surfaces métalliques en zinc, magnésium ou aluminium, ou en un alliage de zinc, de magnésium ou d'aluminium, et sur lesquelles on appliquera, après le traitement, des laques, des revêtements plastiques, des peintures, des mastics ou des adhésifs, caractérisé par le fait que l'on traite les surfaces métalliques, à une température comprise dans l'intervalle allant de 10 à 100 °C, par immersion, pulvérisation ou passage de rouleau, avec une solution aqueuse ayant un pH valant de 2 à 13 et contenant de 10-5 à 1 mole/litre d'un ou de plusieurs composés de type XYZ, où Y représente un groupe alkyle à chaîne linéaire, non-ramifiée, comportant 10 à 20 atomes de carbone, X représente un groupe COOH-, HSO3-, HSO4-, (OH)2PO-, (OH)2PO2-, (OH)(OR')PO- ou (OH)(OR')PO2-, et où Z représente un groupe OH-, SH-, NH2-, NHR', CN-, CH2=CH-, OCN-, époxy-, CH2=CR"-COO-, acrylamido-, (OH)2PO-, (OH)2PO2-, (OH)(OR')PO- ou (OH)(OR')PO2-, où R' représente un groupe alkyle en C1-4, R" représente un atome d'hydrogène ou un groupe alkyle en C1-4, et les groupes X et Z sont liés au groupe Y par leurs extrémités, laquelle solution aqueuse n'est pas employée sur des feuilles d'aluminium en tant que solution d'apprêt réactif (peinture primaire réactive monocomposant) contenant une résine artificielle.
  2. Procédé selon la revendication 1, caractérisé par le fait que, dans la solution aqueuse, de 0,1 à 50 % de l'eau sont remplacés par un alcool en C1-4, de l'acétone, du dioxane ou du tétrahydrofurane.
  3. Procédé selon la revendication 1 ou 2, caractérisé par le fait que la solution aqueuse contient un ou plusieurs composés de type XYZ en une concentration comprise dans l'intervalle de la concentration micellaire critique.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé par le fait que la solution aqueuse contient un agent anti-mousse et/ou un agent solubilisant, chacun en une concentration comprise entre 0,05 et 5 % en poids.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé par le fait que les composés de type XYZ sont sous forme de sels dans la solution aqueuse.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé par le fait que Y représente un groupe alkyle en C10-12 linéaire, non-ramifié.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé par le fait que X représente un groupe (OH)2PO2- ou un groupe (OH)(OR')PO2-.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé par le fait que Z représente un groupe (OH)2PO2-, (OH)(OR')PO2-, OH-, SH-, NHR'-, CH2=CH- ou CH2=CR"-COO-.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé par le fait que la solution aqueuse contient, en tant que composé de type XYZ, de l'acide 12-mercaptododécane-1-phosphonique, de l'acide 12-(N-éthyl-amino)dodécane-1-phosphonique, de l'acide 12-dodécène-1-phosphonique, de l'acide 1,10-décanediphosphonique, de l'acide 1,12-dodécanediphosphonique, de l'acide 12-hydroxydodécane-1-phosphorique, de l'acide 12-(N-éthylamino)dodécane-1-phosphorique, de l'acide 12-dodécène-1-phosphorique, de l'acide 12-mercaptododécane-1-phosphorique, de l'acide 1,10-décanediphosphorique, de l'acide 1,12-dodécanediphosphorique, ou de l'acide 12-acrylododécane-1-phosphorique.
  10. Procédé selon l'une des revendications 1 à 9, caractérisé par le fait que le temps d'immersion est compris entre 5 secondes et 20 minutes, le temps de pulvérisation entre 5 secondes et 15 minutes et le temps de passage de rouleau entre 2 et 120 secondes.
  11. Procédé selon les revendications 1 à 10, caractérisé par le fait que les surfaces métalliques sont soumises, avant application de la solution aqueuse, à une attaque alcaline et/ou acide et sont ensuite rincées avec de l'eau.
  12. Procédé selon les revendications 1 à 11, caractérisé par le fait que les surfaces métalliques sur lesquelles on applique la solution aqueuse par immersion ou pulvérisation, sont ensuite rincées avec de l'eau et éventuellement séchées dans un courant d'azote ou d'air, la température du courant d'azote ou d'air étant comprise entre 15 et 150 °C.
EP97954820A 1996-12-28 1997-12-18 Procede de traitement de surfaces metalliques Expired - Lifetime EP0948666B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19654642 1996-12-28
DE19654642A DE19654642C2 (de) 1996-12-28 1996-12-28 Verfahren zur Behandlung metallischer Oberflächen mit einer wässerigen Lösung
PCT/EP1997/007100 WO1998029580A1 (fr) 1996-12-28 1997-12-18 Procede de traitement de surfaces metalliques

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EP0948666B2 true EP0948666B2 (fr) 2007-09-26

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JP2001508499A (ja) 2001-06-26
TR199901466T2 (xx) 1999-10-21
AU735281B2 (en) 2001-07-05
CA2275729C (fr) 2007-09-25
ES2195202T3 (es) 2003-12-01
KR100487855B1 (ko) 2005-05-09
DE19654642C2 (de) 2003-01-16
WO1998029580A1 (fr) 1998-07-09
EP0948666B1 (fr) 2003-03-19
NO326333B1 (no) 2008-11-10
CA2275729A1 (fr) 1998-07-09
BR9713638A (pt) 2000-04-11
ATE234948T1 (de) 2003-04-15
EP0948666A1 (fr) 1999-10-13
DK0948666T4 (da) 2008-01-07
NO993118D0 (no) 1999-06-23
DK0948666T3 (da) 2003-07-07
DE59709588D1 (de) 2003-04-24
KR20000062344A (ko) 2000-10-25
ES2195202T5 (es) 2008-04-01
US6436475B1 (en) 2002-08-20
NO993118L (no) 1999-06-23
AU6205898A (en) 1998-07-31
JP3986092B2 (ja) 2007-10-03
DE19654642A1 (de) 1998-09-17

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