EP0948666A1 - Procede de traitement de surfaces metalliques - Google Patents

Procede de traitement de surfaces metalliques

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Publication number
EP0948666A1
EP0948666A1 EP97954820A EP97954820A EP0948666A1 EP 0948666 A1 EP0948666 A1 EP 0948666A1 EP 97954820 A EP97954820 A EP 97954820A EP 97954820 A EP97954820 A EP 97954820A EP 0948666 A1 EP0948666 A1 EP 0948666A1
Authority
EP
European Patent Office
Prior art keywords
group
acid
aqueous solution
metallic surfaces
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97954820A
Other languages
German (de)
English (en)
Other versions
EP0948666B1 (fr
EP0948666B2 (fr
Inventor
Hans-Jürgen P. ADLER
Christian Bram
Ralf Feser
Evelin JÄHNE
Christian Jung
Iris MÄGE
Jürgen Rudolph
Lars Sebralla
Martin Stratmann
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.)
Chemetall GmbH
Original Assignee
Chemetall GmbH
Metallgesellschaft AG
Priority date (The priority date 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 date listed.)
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Publication date
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Application filed by Chemetall GmbH, Metallgesellschaft AG filed Critical Chemetall GmbH
Publication of EP0948666A1 publication Critical patent/EP0948666A1/fr
Publication of EP0948666B1 publication Critical patent/EP0948666B1/fr
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Classifications

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

Definitions

  • the invention relates to a method for the treatment of metallic surfaces which consist of zinc, magnesium or aluminum or of the alloys of zinc, magnesium or aluminum and to which lacquers, plastic layers, paints, sealants or adhesives are applied after the treatment .
  • the conversion treatment of aluminum surfaces is still carried out today by yellow chromating, using an acid chromate solution with a pH of 1 to 2, which forms a protective layer on the aluminum.
  • the protective layer consists of an insoluble one
  • Aluminum-chromium (III) mixed oxide causes the high passivity of the surface against corrosion.
  • the residual content of unused chromate ions deposited in the oxide layer additionally causes one
  • DE-A 31 37 525 discloses a method for inhibiting corrosion in an aqueous system, in which 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 with a concentration of 0.1 to 20 ppm. Corrosion problems in cooling systems in particular are to be avoided with the known aqueous system.
  • hydroxyethylidene diphosphonic acid and its inorganic salts are particularly 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, combined with one another or together with other known corrosion inhibitors.
  • the compounds are generally added to aqueous, aqueous-alcoholic, alcoholic and / or oil-containing media.
  • they can be used as corrosion inhibitors in the heat transfer media of cooling or heating circuits, cooling lubricants, mineral oils or savings.
  • the corrosion of metals, in particular of copper and its alloys is prevented by adding the compounds and / or their salts to the media or circulating liquids mentioned.
  • the benzimidazolyl-2-alkane-phosphonic acids contain a phosphonic acid group, a straight-chain or branched, saturated or unsaturated, bivalent, optionally substituted hydrocarbon radical with 1 to 15 carbon atoms and a substituted benzimidazole radical, the straight-chain or branched hydrocarbon radical and the benzimidazole radical being in position 2 of the benzimidazole residue are linked together.
  • aqueous solution for the treatment of zinc, zinc alloys or cadmium which contains nitric acid, an oxidizing agent (H 2 0 2 , nitrate, nitrite, chlorate) and a diphosphonic acid, the two phosphonic acid groups via one Carbon atom are connected to each other, which also has an OH group and an alkyl radical having 1 to 4 carbon atoms.
  • An aqueous solution containing amines, aminal alcohols, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates or ammonia is used to produce the hydroxide layer.
  • a solution is used to produce the second layer, in which the phosphinic and phosphonic acids are present in a concentration of 0.001 mol / l up to the saturation concentration and which contains water, an alcohol or an organic solvent as solvent.
  • the phosphinic and phosphonic acids contain, 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 is said to 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 consisting of zinc, magnesium or aluminum or of the alloys of zinc, magnesium or aluminum are treated in order to give the metallic surfaces in particular good adhesion for Varnishes, plastic layers, paints, sealants and Giving adhesives and protecting the metallic surfaces against corrosion.
  • the effect of the process according to the invention is based on the ability of the compounds XYZ to organize themselves spontaneously and to form very thin, closed films on metallic surfaces, with in particular an orientation of the acidic groups in The direction of the metallic surface takes place and a chemical bond is formed between the hydroxyl groups on the metallic surface and the acidic groups of the compound XYZ.
  • the structure of the compounds XYZ was chosen according to the invention in such a way that there is both a reactive bond of the thin film to the metal surface and to the matrix of lacquers, plastic coatings, paints, sealants and adhesives.
  • the straight chain organic group Y acts as a "spacer" between the groups X and Z; it gives the compound XYZ quasi the properties of a surfactant, since the organic group Y has hydrophobic properties.
  • Group Z gives the coated surface good wettability and reactivity to paints, plastic coatings, paints, sealants and adhesives. If lacquers, 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 paints.
  • 0.1 to 50% of the water in the aqueous solution is replaced by an alcohol having 1 to 4 carbon atoms, by acetone, by dioxane or by tetrahydrofuran.
  • organic solvents result in a higher solubility of the compounds XYZ, which are generally larger molecules, the solubility of which is not very high in pure water.
  • the solution always contains a large amount of water, so that one can still speak of an aqueous system even in the presence of organic solvents.
  • the aqueous solution contains one or more compounds of the type XYZ in a concentration which is in the range of the critical micelle formation concentration.
  • the critical micelle formation concentration cc is a concentration which is characteristic of the respective surfactant and at which the aggregation of the surfactant molecules to micelles starts. The aggregation is reversible. Below the cmc, ie when the solutions are diluted, the micelles break down again into monomeric surfactant molecules.
  • the numerical value of the cmc for each surfactant depends on its constitution and on external parameters such as ionic strength, temperature and concentration of additives. Suitable methods for determining the cmc u. a. Surface tension measurements. With the help of the ring or plate method, the surface tension ⁇ of a surfactant solution is dependent on it
  • the aqueous solution contains a defoamer and / or a solubilizer in each case in an amount of 0.05 to 5% by weight.
  • 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. Amino alcohols, for example, can be used both as defoamers and as solubilizers.
  • the compounds of the type XYZ are present as salts in the aqueous solution.
  • the salts are usually more soluble than the compounds themselves, and also the dissolved salts are very stable, so that the handling of the solution according to the invention is improved by using the salts of the compounds XYZ.
  • the sodium and potassium salts are used in particular.
  • Y is an unbranched, straight-chain alkyl group having 2 to 20 C atoms, or an unbranched, straight-chain group consisting of 1 to 4 aromatic C 6 H 4 nuclei connected in the p-position, or a group which consists of one or two unbranched, straight-chain alkyl radicals each having 1 to 12 carbon atoms and 1 to 4 aromatic C 6 H 4 nuclei connected in the p-position.
  • All groups Y according to the invention are thus characterized by a straight-chain, unbranched molecular structure which is ideally suited to act as a "spacer" between the groups X and Z.
  • the groups Y can therefore have the following structure according to the invention:
  • Y is an unbranched, straight-chain alkyl group having 10 to 12 carbon atoms or a p-CH 2 -C 4 H 6 -CH 2 group or a p, p'- C 6 H 4 - C 6 H 4 group.
  • These groups Y give the compounds XYZ according to the invention very good adhesion-promoting properties for lacquers and other organic coatings.
  • Compounds of the type XYZ, which are equipped with the aforementioned groups X and Z, also have good adhesion-promoting properties for paints and plastic coatings and also form a firm chemical bond with the metallic surfaces.
  • Aqueous solutions which contain the compounds of type XYZ mentioned below have very good adhesion-promoting and corrosion-inhibiting properties: 1-phosphonic acid-12-mercaptododecane, 1-phosphonic acid-12- (N-ethylamino) odecan, 1-phosphonic acid-12-dodecene, p-xylylenediphosphonic acid, 1, 10-decanediphosphonic acid, 1,12-dodecanediphosphonic acid, l-phosphoric acid-12-hydroxvdodecane, l-phosphoric acid-12 (N-ethylamino) dodecane, l-phosphoric acid-12-mercaptododecane,
  • the aqueous solution is applied to the metallic surfaces by dipping, spraying or rolling at 10 to 100 ° C., the dipping time being 5 seconds to 20 minutes, the spraying time 5 seconds to 15 Minutes and the rolling time is 2 to 120 seconds. It has been shown that a thin film is formed on the metallic surfaces when the aqueous solution is immersed, sprayed or rolled is applied, wherein rinsing of the treated metallic surfaces is not absolutely necessary, but can be advantageous.
  • the metallic surfaces are alkali and / or acid pickled before the aqueous solution is applied and then rinsed with water.
  • the water used can be desalinated or not.
  • the metallic surfaces consisting of zinc, magnesium, aluminum and their alloys are always covered by oxide layers and additionally contaminated by the surface adsorption of carbon dioxide, water and / or hydrocarbons. These contaminated top layers are unable to permanently bind paints, plastic coatings, paints, sealants and adhesives and to ensure long-term corrosion protection. Therefore, the metallic surfaces are cleaned in the manner according to the invention before treatment with the aqueous solution.
  • the metallic surfaces to which the aqueous solution has been applied by dipping or spraying are then rinsed with water and optionally dried in a stream of nitrogen or air, the Temperature of the nitrogen or air flow is 15 to 150 ° C. Rinsing and drying do not hinder the formation of the thin film on the metallic surfaces.
  • the water used for rinsing can be desalinated or not.
  • the method according to the invention is used for the treatment of metallic surfaces, to which a cathodic or anodic electro-dip coating, a powder coating, a coil coating coating, a low-solvent high-solid coating or a coating diluted with water is then applied .
  • the pretreatment of the metallic surfaces with the aqueous solution according to the invention has proven particularly useful in all painting processes.
  • Sheets are used as the substrate, which from the
  • the sheets are immersed in an alkaline pickling solution containing 32 g / 1 NaOH and 8 g / 1 Na 2 CO 3 at room temperature for 3 minutes. Then it is rinsed with deionized water. Then the alkaline pickled sheets are immersed for 3 minutes at 40 ° C. in an acid pickling solution which contains 10 g / 1 H 2 SO 4 and 33 g / 1 H 2 0 2 . Then it is rinsed with deionized water. Finally, the pickled sheets are immersed at 40 ° C. for 3 minutes in the aqueous solution according to the invention which contains the compound XYZ according to the invention in a concentration of approximately 10 "3 mol / 1. This is followed by rinsing with demineralized water and drying at room temperature in nitrogen flow.
  • the sheets are first sprayed at 65 ° C. for 10 seconds with an alkaline pickling solution which contains 10 g / 1 Bonder V338M ® . The sheets are then rinsed by spraying them with water. The alkaline pickled sheets are then sprayed at 50 ° C. for 30 seconds with an acid pickling solution containing 16 g / 1 Bonder V450M ® . The pickled sheets are then rinsed by spraying them with deionized 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 demineralized water and drying in an air stream at room temperature. The compound XYZ according to the invention is present in the aqueous solution in a concentration of about 10 "3 mol / 1. ( ® registered trademark of Metallgesellschaft AG, Frankfurt / Main, DE)
  • the sheets are alkali and acid pickled and rinsed according to the spray process.
  • the aqueous solution according to the invention is applied to the sheets. rolled on at room temperature for two seconds, the roll being driven at 25 rpm.
  • the compound XYZ is present in the aqueous solution according to the invention in a concentration of approximately 10 "3 mol / 1.
  • the metal sheets are dried in a forced air oven at 105.degree.
  • Aqueous solutions containing the following compounds XYZ were used to carry out the process variants: l-phosphonic acid-12- (N-ethylamino) dodecane 1-phosphoric acid-12-hydroxydodecane p-xylylenediphosphonic acid 1, 12-dodecanediphosphonic acid
  • the sheets treated with the aqueous solution according to the invention were painted by various methods. Both a cathodic electrodeposition paint and a powder paint and also a polyester paint were used.
  • the electrocoat material was electrolytically deposited on the metal sheets at a voltage of approximately 250 volts and then dried at 180 ° C. for 22 minutes.
  • the powder coating was applied to the sheets by electrostatic spraying and then dried at 200 ° C. for 10 minutes.
  • the polyester paint system consisted of a primer and a top coat. Both components were applied to the sheets by squeegees.
  • the primer had a layer thickness of 5 ⁇ m, while the top coat had a layer thickness of 25 ⁇ m.
  • the baking temperatures were 216 ° C for the primer and 241 ° C for the top coat.
  • Example 2 Example 2:
  • the following table contains the test results which were measured using different substances according to the invention.
  • the substances were present in the solutions according to the invention in a concentration of approximately 10 "3 mol / l.
  • the salt spray test ESS reinforced with acetic acid, shows that the thin films produced according to the invention ensure very good protection against infiltration compared to the comparison sheets; only that of the comparison sheets The chromated sheet is adequately protected against corrosion
  • the T-bend test which was carried out under the T 0 condition, and the cross-cut with Erichsen indentation show that the paint adhesion on the sheets treated according to the invention is better than on the comparison sheets Results achieved with the invention are surprisingly good, since they are equivalent to the result obtained with chromating in terms of corrosion resistance and clearly superior in terms of paint adhesion.
  • ARXPS X-ray photoelectron spectroscopy
  • FIG. 1 shows the X-ray photoelectron spectrum of the 1-phosphoric acid-12- (N-ethylamino) dodecane on the AlMgl alloy, in which the XPS intensity ratio N / P is shown as a function of the angle ⁇ , where N is the intensity of the Nls peak Amino group and P der
  • P2s peak is the phosphoric acid group and is the abbreviation XPS for the term
  • HDLS OH- (CH 2 ) ⁇ l -COOH
  • HDPS (OH) 2 P0 2 - (CH.) 12 -OH

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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)

Abstract

L'invention concerne un procédé permettant de traiter des surfaces métalliques qui sont constituées de zinc, de magnésium ou d'aluminium ou bien d'un alliage de zinc, de magnésium ou d'aluminium, surfaces sur lesquelles sont appliqués, après le traitement, des laques, des couches de matière synthétique, des peintures, des mastiques d'étanchéité ou des adhésifs. Le traitement des surfaces métalliques se fait à une température pouvant aller de 10 à 100 °C, par immersion, pulvérisation ou laminage avec une solution aqueuse. Cette solution présente un pH pouvant aller de 2 à 13 et contient un ou plusieurs composés du type XYZ, à une concentration de 10-5 à 1 mol/l. Y représente un groupe organique qui possède 2 à 50 atomes de C et présente une structure à chaîne droite. X représente un groupe COOH, HSO¿3?, HSO4, (OH)2PO, (OH)2PO2, (OH) (OR') PO ou bien OH (OR') PO2. Z représente un groupe OH, SH, NH2, NHR', CN, CH=CH2, OCN, époxy, CH?2¿=CR''-COO, amide d'acide acrylique, COOH, (OH)¿2?PO, (OH)2PO2, (OH) (OR') PO ou bien (OH) (OR') PO2. R' représente un groupe alkyle ayant 1 à 4 atomes de C. R'' représente un atome de H ou un groupe alkyle ayant 1 à 4 atomes de C. Les groupes X et Z sont chacun reliés au groupe Y par leur position terminale.
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
DE19654642A DE19654642C2 (de) 1996-12-28 1996-12-28 Verfahren zur Behandlung metallischer Oberflächen mit einer wässerigen Lösung
DE19654642 1996-12-28
PCT/EP1997/007100 WO1998029580A1 (fr) 1996-12-28 1997-12-18 Procede de traitement de surfaces metalliques

Publications (3)

Publication Number Publication Date
EP0948666A1 true EP0948666A1 (fr) 1999-10-13
EP0948666B1 EP0948666B1 (fr) 2003-03-19
EP0948666B2 EP0948666B2 (fr) 2007-09-26

Family

ID=7816377

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97954820A Expired - Lifetime EP0948666B2 (fr) 1996-12-28 1997-12-18 Procede de traitement de surfaces metalliques

Country Status (14)

Country Link
US (1) US6436475B1 (fr)
EP (1) EP0948666B2 (fr)
JP (1) JP3986092B2 (fr)
KR (1) KR100487855B1 (fr)
AT (1) ATE234948T1 (fr)
AU (1) AU735281B2 (fr)
BR (1) BR9713638A (fr)
CA (1) CA2275729C (fr)
DE (2) DE19654642C2 (fr)
DK (1) DK0948666T4 (fr)
ES (1) ES2195202T5 (fr)
NO (1) NO326333B1 (fr)
TR (1) TR199901466T2 (fr)
WO (1) WO1998029580A1 (fr)

Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7815963B2 (en) 1996-10-17 2010-10-19 The Trustees Of Princeton University Enhanced bonding layers on titanium materials
US7396594B2 (en) * 2002-06-24 2008-07-08 The Trustees Of Princeton University Carrier applied coating layers
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TR199901466T2 (xx) 1999-10-21
EP0948666B1 (fr) 2003-03-19
DE59709588D1 (de) 2003-04-24
NO326333B1 (no) 2008-11-10
JP2001508499A (ja) 2001-06-26
NO993118D0 (no) 1999-06-23
ES2195202T5 (es) 2008-04-01
BR9713638A (pt) 2000-04-11
DK0948666T3 (da) 2003-07-07
EP0948666B2 (fr) 2007-09-26
WO1998029580A1 (fr) 1998-07-09
CA2275729C (fr) 2007-09-25
AU735281B2 (en) 2001-07-05
NO993118L (no) 1999-06-23
US6436475B1 (en) 2002-08-20
JP3986092B2 (ja) 2007-10-03
DK0948666T4 (da) 2008-01-07
KR20000062344A (ko) 2000-10-25
ATE234948T1 (de) 2003-04-15
DE19654642C2 (de) 2003-01-16
CA2275729A1 (fr) 1998-07-09
AU6205898A (en) 1998-07-31
ES2195202T3 (es) 2003-12-01
DE19654642A1 (de) 1998-09-17
KR100487855B1 (ko) 2005-05-09

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