EP0672467B1 - Process for modification of metallic surfaces - Google Patents

Process for modification of metallic surfaces Download PDF

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Publication number
EP0672467B1
EP0672467B1 EP95103462A EP95103462A EP0672467B1 EP 0672467 B1 EP0672467 B1 EP 0672467B1 EP 95103462 A EP95103462 A EP 95103462A EP 95103462 A EP95103462 A EP 95103462A EP 0672467 B1 EP0672467 B1 EP 0672467B1
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sample
metal surfaces
acid
immersed
cleaned
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German (de)
French (fr)
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EP0672467A1 (en
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Harald Dr. Keller
Gerhard Dr. Hoffmann
Walter Denzinger
Rainer Dr. Fässler
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BASF SE
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BASF SE
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B05D3/102—Pretreatment of metallic substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies

Definitions

  • the present invention relates to a method for modification of cleaned or chemically pretreated metal surfaces with aqueous solutions of organic polymers and use the modified metal surfaces for painting, in particular for cathodic electrocoating.
  • the phosphating of iron and iron alloys is general Common method to check the corrosion resistance of the Increase metal and improve the adhesion to a paint job.
  • Electrodeposition coating is generally carried out on phosphated Underground. Improved paint adhesion, in particular The electrocoat is often modified reached the phosphating baths (see e.g. DE-A 22 32 067, Japanese Patent Application No. 58 144 477 (Chemical Abstracts 99/216843) and DE-A 34 08 577).
  • EP-A-0 274 738 describes a process for the production of hydrophilic Coatings on aluminum surfaces to improve the Corrosion resistance is known, when you look at the aluminum surfaces an aqueous solution or dispersion of a special amphoteric (meth) acrylamide copolymer, which in addition to (meth) acrylamide unsaturated cationic and unsaturated contains incorporated anionic monomers, applies.
  • a hint for the treatment of metal surfaces to improve paint adhesion cannot be found in this publication.
  • the object of the present invention is to be cleaned by a Metal surfaces or on industrial ones Conversion layers additionally applied thin polymer layer to significantly improve the paint adhesion and in this way a improved protection, in particular reduced rust infiltration to get the coating.
  • this task can be particularly advantageous solve that the cleaned or chemically pretreated Metal surface with a thin layer of an amino group containing Polymer is coated.
  • the present invention relates to a method for modification of cleaned or chemically pretreated metal surfaces with aqueous solutions of organic polymers, the result is characterized in that the cleaned or chemically pretreated Metal surfaces with an aqueous solution of amino groups containing organic polymers are treated.
  • Treatment with aqueous solution of the amino group-containing organic polymers can be by casting, spraying or Diving done.
  • the metal surfaces are particularly such of iron, iron alloys, zinc, aluminum, copper, cobalt, Nickel or manganese, preferably also chemically pretreated Metal surfaces, especially metal surfaces with Phosphate conversion layers, optionally with water or Chromate solution rinsed, can be used.
  • Organic polymers containing amino groups for the process according to the invention are preferably hydrolysis products of polymers which have units of the general formula (I) contain or consist of, wherein R 1 and R 2 are identical or different from one another and represent H or alkyl having 1 to 6 carbon atoms.
  • the present invention also relates to the use the modified according to the inventive method Metal surfaces for painting, especially for the cathodic electrocoating.
  • the metal surfaces modified by the process according to the invention are characterized by significantly improved corrosion protection which, in particular, after electrodeposition painting, especially a cathodic electrodeposition coating identifies.
  • the metal surfaces to be modified come for Process according to the invention those made of iron, iron alloys, Steel, zinc, aluminum, copper, cobalt, nickel and manganese in Question that is either cleaned (degreased) or chemically pretreated, e.g. can be phosphated and / or chromated.
  • the application of the organic polymer containing amino groups is generally carried out from an aqueous solution, for example by Pouring, spraying, dipping and then drying the modified in this way Metal surfaces.
  • Suitable organic polymers containing amino groups are preferably amino group-containing hydrolysis products of polymers which have structural units of the general formula (I) contain or consist thereof, wherein R 1 and R 2 are identical or different from each other and for hydrogen or alkyl having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl , n-hexyl, isohexyl or cyclohexyl.
  • R 1 and R 2 are identical or different from each other and for hydrogen or alkyl having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl , n-hexyl, isohexyl or cyclohexyl.
  • hydrolysis products examples include hydrolysis products of homo- and copolymers of N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl propionamide and N-vinyl-N-methyl propionamide, N-vinylformamide being preferred as being very easily hydrolyzable is.
  • Comonomers are monoethylenically unsaturated Carboxylic acids with 3 to 8 carbon atoms and the water-soluble salts of these monomers into consideration.
  • This group of comonomers includes, for example, acrylic acid, Methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, Citraconic acid, methylene malonic acid, allylacetic acid, vinyl acetic acid, Crotonic acid, fumaric acid, mesaconic acid and itaconic acid. From this group of monomers, preference is given to acrylic acid, Methacrylic acid, maleic acid or mixtures of the above Carboxylic acids, especially mixtures of acrylic acid and maleic acid or mixtures of acrylic acid and methacrylic acid.
  • the Comonomers can either be in the form of free carboxylic acids or in partially or completely neutralized form during the copolymerization be used.
  • To neutralize the monoethylenic unsaturated carboxylic acids can for example Alkali metal, alkaline earth metal bases, ammonia or amines, e.g. Sodium hydroxide solution, potassium hydroxide solution, soda, potash, sodium hydrogen carbonate, Magnesium oxide, calcium hydroxide, calcium oxide, ammonia, triethylamine, Ethanolamine, diethanolamine, triethanolamine, morpholine, Diethylene triamine or tetraethylene pentamine can be used.
  • Alkali metal, alkaline earth metal bases, ammonia or amines e.g. Sodium hydroxide solution, potassium hydroxide solution, soda, potash, sodium hydrogen carbonate, Magnesium oxide, calcium hydroxide, calcium oxide, ammonia, triethylamine, Ethanolamine, diethanolamine, triethanolamine, morpholine, Diethylene triamine or tetraethylene pentamine can be used.
  • esters, amides and nitriles of the above carboxylic acids e.g. Acrylic acid methyl esters, Ethyl acrylate, n- and isopropyl acrylate, N- and isobutyl acrylate, hexyl acrylate, Methyl methacrylate, methyl methacrylate, butyl methacrylate, Hydroxyethyl acrylate, hydroxypropyl acrylate, Hydroxybutyl acrylate, hydroxyisobutyl acrylate, hydroxyethyl methacrylate, Hydroxypropyl methacrylate, hydroxyisobutyl methacrylate, Monomethyl maleate, dimethyl maleate, monoethyl maleate, Maleic acid diethyl ester, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylamide, methacrylamide, N-dimethylacrylamide,
  • Monomers acrylamidoglycolic acid, vinylsulfonic acid, allylsulfonic acid, Methallylsulfonic acid, styrene sulfonic acid, acrylic acid (3-sulfopropyl) ester, Methacrylic acid (3-sulfopropyl) ester and acrylamidomethylpropanesulfonic acid and phosphonic acid groups containing monomers such as vinyl phosphate, allyl phosphate and acrylamidomethyl propanephosphonic acid.
  • N-vinylpyrrolidone N-vinylcaprolactam
  • N-vinylimidazole N-vinyl-2-methylimidazoline
  • Diallyl ammonium chloride vinyl acetate and vinyl propionate. It is of course also possible to mix the use mentioned monomers, for example for improvement of liability.
  • the copolymers should be at least 20% by weight, preferably at least Polymerized 50% by weight of N-vinylamides.
  • the copolymers can be prepared by known processes, e.g. solution, precipitation, suspension or emulsion polymerization using compounds operating under the polymerization conditions Form radicals, take place.
  • the polymerization temperatures are usually in the range from 30 to 200, preferably 40 to 110 ° C.
  • Suitable initiators are, for example, azo and peroxy compounds and the usual Redox initiator systems, such as combinations of hydrogen peroxide and reducing compounds, e.g. Sodium sulfite, Sodium bisulfite, sodium formaldehyde sulfoxylate and Hydrazine. If necessary, these systems can additionally contain small amounts of a heavy metal salt.
  • the homo- and copolymers to be used according to the invention have generally K values from 7 to 300, preferably 10 to 250. Die According to H. Fikentscher, K values can be measured in aqueous solution at 25 ° C, at concentrations between 0.1% and 5% depending on the K value lie, be measured.
  • the homopolymers or copolymers of the general described above Formula (I) are done by the action of acids or bases modified that as a result of this treatment the formyl group from the polymerized N-vinylformamide to form is split off from amine or ammonium groups.
  • the solvolysis temperatures are usually in the range from 20 to 100 ° C, preferably 70 to 90 ° C.
  • Suitable acids are, for example Carboxylic acids such as formic acid, acetic acid or propionic acid, a Sulfonic acid such as benzenesulfonic acid or toluenesulfonic acid or an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid.
  • Suitable bases are sodium hydroxide solution or potassium hydroxide solution and ammonia, Amines and alkaline earth metal bases such as calcium hydroxide.
  • the usual methods are used to desalt the polymers such as ion exchangers, electrodialysis or ultrafiltration.
  • the method according to the invention is particularly suitable for treatment of iron, iron alloys and chemically pretreated Substrate, such as phosphated and possibly with water or chromate solution rinsed metal surfaces suitable. It is suitable but also for the surface modification of zinc, aluminum, Copper, cobalt, nickel and manganese.
  • aqueous polymer solution is applied as already mentioned above, expediently by dipping, pouring or Spraying.
  • Polymer solutions can be used for the process according to the invention Solids content between 0.01 and 5, preferably between 0.1 and 1 wt .-% used in the temperature range between 20 and 80 ° C. become.
  • the modification of the metal surface by the amino groups containing organic polymer could be determined by secondary ion mass spectrometry (TOF-SIMS) and atomic force microscopy (RKM) to prove.
  • TOF-SIMS secondary ion mass spectrometry
  • RKM atomic force microscopy
  • the modified metal or with the inventive method chemically pretreated metal surfaces are suitable in principle for all purposes, for chemically pretreated metal surfaces are suitable.
  • the polymer layers cause an unusually strong improvement the resistance of the paint film to rust infiltration with corrosive stress. This advantage becomes special with cathodic electrocoating, which is why the process is particularly advantageous for this type of painting is applied.
  • the invention has practical application Procedure e.g. for modification of phosphated car bodies.
  • Test sheets measuring 190 ⁇ 105 ⁇ 0.75 mm were immersed in aqueous polyvinylamine solutions (K value 30) for 1 minute each.
  • the concentrations of the polymer solutions were 0.01; 0.1; 1 and 2 %.
  • the bath temperature was 23 ° and 50 ° C, see. Table. After drying in air, the sheets were immersed in deionized water for a further 5 seconds and dried again in air.
  • the pretreated test panels were used to further test the effect coated with an electrocoat.
  • the rust at the Ritz was used as a measure of the adhesion of the paints certainly.
  • a 0.1 mm wider was made on the steel sheets Longitudinal section, on the sheets with a phosphate conversion layer a 0.1 mm wide cross cut carved into the paintwork, that reached down to the sheet metal surface.
  • the painted steel sheets were then 15 days in the salt spray test (40 ° C, 5% NaCl solution: DIN 50 021) for corrosion resistance checked.
  • the painted steel sheets with a phosphate conversion layer were tested in the salt water soak test. For this the test plate was heated for 10 days in a 5% solution heated to 55 ° C NaCl solution immersed.
  • Degreased body steel sheet (e.g. St 1405) was as above specified in aqueous polyvinylamine solutions of various concentrations immersed, treated and electrocoated.
  • a manganese-modified low-zinc-phosphated coating on both sides (Spray process) and then rinsed with water Steel sheet (BONDER® 26 W OC) was poured into aqueous as indicated above Immersed polyvinylamine solutions of various concentrations and processed further.
  • the extent of the rust is reduced by the adhesion-promoting Polymer layer in the samples with a phosphate conversion layer by two to three times.
  • the method according to the invention completely prevents rust formation.
  • the entire appearance of the paint surface also shows through the method according to the invention compared to a significant improvement the state of the art. While the lacquered surfaces of the reference samples show strong blistering, the paint surface is on the metal surface modified with aqueous polyvinylamine solution perfect.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Chemically Coating (AREA)

Abstract

Method of modifying cleaned or chemically pre-treated metal surfaces with aq. solns. of organic polymers contg. amino gps. In an example, a sample of Mn-modified, low Zn content, phosphatised steel that had been cleaned with water was immersed for 60s in a 0.1 wt.% aq. polyvinylamine soln. at 50 deg.C, then after drying in air the sample was immersed for 5s in deionised water and then after drying in air again the sample was cathodically electro-plated in a bath according to the comparative example in German patent application DE4208056-A2. The sample was plated at 320-380 V to give a 23 micron thick coating, and then fired for 25 mins. at 165 deg.C. A 0.1 mm wide incision was made in the lacquered sample, extending down to the metal surface and the sample was sprayed for 15 days with aq. NaCl soln. (5 wt.%) at 40 deg.C (salt water spray test), whilst another sample was immersed for 10 days in an aq. NaCl soln. (5 wt.%) warmed to 55 deg.C (salt water soak test). No rust was observed for the soak test, whilst only a slight amt. of rust was observed for the spray test.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Modifizierung von gereinigten oder chemisch vorbehandelten Metalloberflächen mit wäßrigen Lösungen organischer Polymerer und die Verwendung der modifizierten Metalloberflächen zur Lackierung, insbesondere für die kathodische Elektrotauchlackierung.The present invention relates to a method for modification of cleaned or chemically pretreated metal surfaces with aqueous solutions of organic polymers and use the modified metal surfaces for painting, in particular for cathodic electrocoating.

Die Verbesserung der Naßhaftfestigkeit organischer Beschichtungen auf Stahloberflächen, die mit stark verdünnten Lösungen von Polysäuren, wie Polyacryl- und Polymethylenacrylsäure behandelt werden und eine verbesserte Haftung zu Alkyd/Melamin-, Epoxid- und Polyurethanharzen aufweisen, wird von Z. Gao, H. Yamabe, B. Marold und W. Funke in farbe + lack, 98 (1992), Nr. 12, S. 917 beschrieben.The improvement of the wet adhesive strength of organic coatings on steel surfaces covered with highly dilute solutions of polyacids, treated like polyacrylic and polymethylene acrylic acid and improved adhesion to alkyd / melamine, epoxy and Have polyurethane resins is from Z. Gao, H. Yamabe, B. Marold and W. Funke in Farbe + Lack, 98 (1992), No. 12, p. 917 described.

Die Phosphatierung von Eisen und Eisenlegierungen ist eine allgemein gebräuchliche Methode, um die Korrosionsbeständigkeit des Metalls zu erhöhen und die Haftung zu einer Lackierung zu verbessern.The phosphating of iron and iron alloys is general Common method to check the corrosion resistance of the Increase metal and improve the adhesion to a paint job.

Aus der Publikation J. of Coatings Technol. 65 (1993), Nr. 819, S. 59-64 sind auch Phosphatierlösungen mit Polyethylenimin als Additiv bekannt, die Phosphatschichten mit einer niedrigen Permeabilität gegenüber Feuchtigkeit aufweisen.From the publication J. of Coatings Technol. 65 (1993), No. 819, Pp. 59-64 are also phosphating solutions with polyethyleneimine as Additively known, the phosphate layers with a low Have moisture permeability.

Die Elektrotauchlack-Beschichtung erfolgt generell auf phosphatiertem Untergrund. Eine verbesserte Lackhaftung, insbesondere zu den Elektrotauchlacken wird häufig durch eine Modifizierung der Phosphatierungsbäder erreicht (vgl. z.B. DE-A 22 32 067, japanische Patentanmeldung Nr. 58 144 477 (Chemical Abstracts 99/216843) und DE-A 34 08 577).Electrodeposition coating is generally carried out on phosphated Underground. Improved paint adhesion, in particular The electrocoat is often modified reached the phosphating baths (see e.g. DE-A 22 32 067, Japanese Patent Application No. 58 144 477 (Chemical Abstracts 99/216843) and DE-A 34 08 577).

Um die Lackhaftung noch weiter zu erhöhen, werden spezielle passivierende Nachspülungen, beispielsweise Chromatlösungen verwendet (vgl. hierzu auch Dr. Josef Ruf, Organischer Metallschutz: Entwicklung und Anwendung von Beschichtungsstoffen / Josef Ruf - Hannover: Vincentz, 1993, S. 646f).To increase the paint adhesion even more, special passivating rinsing, e.g. chromate solutions used (see also Dr. Josef Ruf, Organic Metal Protection: Development and application of coating materials / Josef Ruf - Hanover: Vincentz, 1993, pp. 646f).

Die Lackhaftung und insbesondere die Korrosionsfestigkeit auf den verwendeten Konversionsschichten genügen jedoch nicht immer den gestellten Anforderungen. The paint adhesion and especially the corrosion resistance on the However, the conversion layers used do not always meet the requirements requirements.

Aus der EP-A-0 274 738 ist ein Verfahren zur Erzeugung von hydrophilen Überzügen auf Aluminiumoberflächen zur Verbesserung der Korrosionsbeständigkeit bekannt, bei dem man auf die Aluminiumoberflächen eine wässrige Lösung oder Dispersion eines speziellen amphoteren (Meth)acrylamid-copolymerisats, welches neben (Meth)acrylamid ungesättigte kationische und ungesättigte anionische Monomere eingebaut enthält, aufbringt. Ein Hinweis auf die Behandlung von Metalloberflächen zur Verbesserung der Lackhaftung ist dieser Druckschrift nicht zu entnehmen. EP-A-0 274 738 describes a process for the production of hydrophilic Coatings on aluminum surfaces to improve the Corrosion resistance is known, when you look at the aluminum surfaces an aqueous solution or dispersion of a special amphoteric (meth) acrylamide copolymer, which in addition to (meth) acrylamide unsaturated cationic and unsaturated contains incorporated anionic monomers, applies. A hint for the treatment of metal surfaces to improve paint adhesion cannot be found in this publication.

Aufgabe der vorliegenden Erfindung ist es, durch eine auf gereinigte Metalloberflächen oder auf industriell eingesetzte Konversionsschichten zusätzlich aufgebrachte dünne Polymerschicht die Lackhaftung wesentlich zu verbessern und auf diese Weise eine verbesserte Schutzwirkung, insbesondere eine verringerte Rostunterwanderung der Beschichtung zu erhalten.The object of the present invention is to be cleaned by a Metal surfaces or on industrial ones Conversion layers additionally applied thin polymer layer to significantly improve the paint adhesion and in this way a improved protection, in particular reduced rust infiltration to get the coating.

Überraschenderweise läßt sich diese Aufgabe besonders vorteilhaft dadurch lösen, daß die gereinigte oder chemisch vorbehandelte Metalloberfläche mit einer dünnen Schicht eines Aminogruppen enthaltenden Polymeren überzogen wird.Surprisingly, this task can be particularly advantageous solve that the cleaned or chemically pretreated Metal surface with a thin layer of an amino group containing Polymer is coated.

Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Modifizieren von gereinigten oder chemisch vorbehandelten Metalloberflächen mit wäßrigen Lösungen organischer Polymerer, das dadurch gekennzeichnet ist, daß die gereinigten oder chemisch vorbehandelten Metalloberflächen mit einer wäßrigen Lösung von Aminogruppen enthaltenden organischen Polymeren behandelt werden.The present invention relates to a method for modification of cleaned or chemically pretreated metal surfaces with aqueous solutions of organic polymers, the result is characterized in that the cleaned or chemically pretreated Metal surfaces with an aqueous solution of amino groups containing organic polymers are treated.

Die Behandlung mit wäßriger Lösung des Aminogruppen enthaltenden organischen Polymeren kann dabei durch Gießen, Sprühen oder Tauchen erfolgen.Treatment with aqueous solution of the amino group-containing organic polymers can be by casting, spraying or Diving done.

Bei den Metalloberflächen handelt es sich insbesondere um solche von Eisen, Eisenlegierungen, Zink, Aluminium, Kupfer, Kobalt, Nickel oder Mangan, wobei vorzugsweise auch chemisch vorbehandelte Metalloberflächen, insbesondere Metalloberflächen mit Phosphatkonversionsschichten, gegebenenfalls mit Wasser oder Chromatlösung nachgespült, eingesetzt werden können.The metal surfaces are particularly such of iron, iron alloys, zinc, aluminum, copper, cobalt, Nickel or manganese, preferably also chemically pretreated Metal surfaces, especially metal surfaces with Phosphate conversion layers, optionally with water or Chromate solution rinsed, can be used.

Als Aminogruppen enthaltende organische Polymere werden für das erfindungsgemäße Verfahren vorzugsweise Hydrolyseprodukte von Polymeren, die Einheiten der allgemeinen Formel (I)

Figure 00030001
enthalten oder daraus bestehen, wobei R1 und R2 untereinander gleich oder verschieden sind und für H oder Alkyl mit 1 bis 6 Kohlenstoffatomen stehen, eingesetzt. Organic polymers containing amino groups for the process according to the invention are preferably hydrolysis products of polymers which have units of the general formula (I)
Figure 00030001
contain or consist of, wherein R 1 and R 2 are identical or different from one another and represent H or alkyl having 1 to 6 carbon atoms.

Gegenstand der vorliegenden Erfindung ist außerdem die Verwendung der nach dem erfindungsgemäßen Verfahren hergestellten modifizierten Metalloberflächen zur Lackierung, insbesondere für die kathodische Elektrotauchlackierung.The present invention also relates to the use the modified according to the inventive method Metal surfaces for painting, especially for the cathodic electrocoating.

Die nach dem erfindungsgemäßen Verfahren modifizierten Metalloberflächen zeichnen sich durch deutlich verbesserten Korrosionsschutz aus, der sich insbesondere nach einer Elektrotauchlackierung, insbesondere einer kathodischen Elektrotauchlackierung ausweist.The metal surfaces modified by the process according to the invention are characterized by significantly improved corrosion protection which, in particular, after electrodeposition painting, especially a cathodic electrodeposition coating identifies.

Im einzelnen ist zum erfindungsgemäßen Verfahren folgendes aus zuführen.In detail, the following is to be performed for the method according to the invention.

Als zu modifizierende Metalloberflächen kommen für das erfindungsgemäße Verfahren solche aus Eisen, Eisenlegierungen, Stahl, Zink, Aluminium, Kupfer, Kobalt, Nickel und Mangan in Frage, die entweder gereinigt (entfettet) oder chemisch vorbehandelt, z.B. phosphatiert und/oder chromatiert sein können.The metal surfaces to be modified come for Process according to the invention those made of iron, iron alloys, Steel, zinc, aluminum, copper, cobalt, nickel and manganese in Question that is either cleaned (degreased) or chemically pretreated, e.g. can be phosphated and / or chromated.

Der Auftrag des Aminogruppen enthaltenden organischen Polymeren erfolgt im allgemeinen aus wäßriger Lösung, beispielsweise durch Gießen, Sprühen, Tauchen und anschließendes Trocknen der so modifizierten Metalloberflächen.The application of the organic polymer containing amino groups is generally carried out from an aqueous solution, for example by Pouring, spraying, dipping and then drying the modified in this way Metal surfaces.

Als Aminogruppen enthaltende organische Polymere eignen sich vorzugsweise Aminogruppen enthaltende Hydrolyseprodukte von Polymeren die Struktureinheiten der allgemeinen Formel (I)

Figure 00040001
enthalten oder daraus bestehen, wobei R1 und R2 untereinander gleich oder verschieden sind und für Wasserstoff oder Alkyl mit 1 bis 6 Kohlenstoffatomen, z.B. Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tert.-Butyl, Amyl, n-Hexyl, Isohexyl oder Cyclohexyl stehen können.Suitable organic polymers containing amino groups are preferably amino group-containing hydrolysis products of polymers which have structural units of the general formula (I)
Figure 00040001
contain or consist thereof, wherein R 1 and R 2 are identical or different from each other and for hydrogen or alkyl having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl , n-hexyl, isohexyl or cyclohexyl.

Beispiele für derartige Hydrolyseprodukte sind Hydrolyseprodukte von Homo- und Copolymeren des N-Vinylformamid, N-Vinyl-N-methylformamid, N-Vinylacetamid, N-Vinyl-N-methylacetamid, N-Vinyl-N-ethylacetamid, N-Vinylpropionamid und N-Vinyl-N-Methylpropionamid, wobei N-Vinylformamid als sehr leicht hydrolisierbar bevorzugt ist. Als Comonomere kommen monoethylenisch ungesättigte Carbonsäuren mit 3 bis 8 C-Atome sowie die wasserlöslichen Salze dieser Monomere in Betracht.Examples of such hydrolysis products are hydrolysis products of homo- and copolymers of N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl propionamide and N-vinyl-N-methyl propionamide, N-vinylformamide being preferred as being very easily hydrolyzable is. Comonomers are monoethylenically unsaturated Carboxylic acids with 3 to 8 carbon atoms and the water-soluble salts of these monomers into consideration.

Zu dieser Gruppe von Comonomeren gehören beispielsweise Acrylsäure, Methacrylsäure, Dimethylacrylsäure, Ethacrylsäure, Maleinsäure, Citraconsäure, Methylenmalonsäure, Allylessigsäure, Vinylessigsäure, Crotonsäure, Fumarsäure, Mesaconsäure und Itaconsäure. Aus dieser Gruppe von Monomeren bevorzugt sind Acrylsäure, Methacrylsäure, Maleinsäure oder auch Mischungen der genannten Carbonsäuren, insbesondere Mischungen aus Acrylsäure und Maleinsäure oder Mischungen aus Acrylsäure und Methacrylsäure. Die Comonomeren können entweder in Form der freien Carbonsäuren oder in partiell oder vollständig neutralisierter Form bei der Copolymerisation eingesetzt werden. Zur Neutralisation der monoethylenisch ungesättigten Carbonsäuren können beispielsweise Alkalimetall-, Erdalkalimetallbasen, Ammoniak oder Amine, z.B. Natronlauge, Kalilauge, Soda, Pottasche, Natriumhydrogencarbonat, Magnesiumoxid, Calciumhydroxyd, Calciumoxid, Ammoniak, Triethylamin, Ethanolamin, Diethanolamin, Triethanolamin, Morpholin, Diethylentriamin oder Tetraethylenpentamin verwendet werden.This group of comonomers includes, for example, acrylic acid, Methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, Citraconic acid, methylene malonic acid, allylacetic acid, vinyl acetic acid, Crotonic acid, fumaric acid, mesaconic acid and itaconic acid. From this group of monomers, preference is given to acrylic acid, Methacrylic acid, maleic acid or mixtures of the above Carboxylic acids, especially mixtures of acrylic acid and maleic acid or mixtures of acrylic acid and methacrylic acid. The Comonomers can either be in the form of free carboxylic acids or in partially or completely neutralized form during the copolymerization be used. To neutralize the monoethylenic unsaturated carboxylic acids can for example Alkali metal, alkaline earth metal bases, ammonia or amines, e.g. Sodium hydroxide solution, potassium hydroxide solution, soda, potash, sodium hydrogen carbonate, Magnesium oxide, calcium hydroxide, calcium oxide, ammonia, triethylamine, Ethanolamine, diethanolamine, triethanolamine, morpholine, Diethylene triamine or tetraethylene pentamine can be used.

Weitere geeignete Comonomere sind beispielsweise die Ester, Amide und Nitrile der oben angegebenen Carbonsäuren, z.B. Acrylsäuremethylestern, Acrylsäureethylester, Acrylsäure-n- und -isopropylester, Acrylsäure-n- und -isobutylester, Acrylsäurehexylester, Methacrylsäuremethylester, Methacrylsäureethylester, Methacrylsäurebutylester, Hydroxyethylacrylat, Hydroxypropylacrylat, Hydroxybutylacrylat, Hydroxyisobutylacrylat, Hydroxyethylmethacrylat, Hydroxypropylmethacrylat, Hydroxyisobutylmethacrylat, Maleinsäuremonomethylester, Maleinsäuredimethylester, Maleinsäuremonoethylester, Maleinsäurediethylester, 2-Ethylhexylacrylat, 2-Ethylhexylmethacrylat, Acrylamid, Methacrylamid, N-Dimethylacrylamid, N-tert.-Butylacrylamid, Acrylnitril, Methacrylnitril, Dimethylaminoethylacrylat, Dimethylaminoethylmethacrylat, Diethylaminoethylacrylat, Diethylaminoethylmethacrylat, die Salze der zuletzt genannten Monomeren mit Carbonsäuren oder Mineralsäuren sowie die quaternierten Produkte. Außerdem eignen sich als Monomere Acrylamidoglykolsäure, Vinylsulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Styrolsulfonsäure, Acrylsäure-(3-sulfopropyl)ester, Methacrylsäure-(3-sulfopropyl)ester und Acrylamidomethylpropansulfonsäure sowie Phosphonsäuregruppen enthaltende Monomere, wie Vinylphosphat, Allylphosphat und Acrylamidomethylpropanphosphonsäure. Other suitable comonomers are, for example, the esters, amides and nitriles of the above carboxylic acids, e.g. Acrylic acid methyl esters, Ethyl acrylate, n- and isopropyl acrylate, N- and isobutyl acrylate, hexyl acrylate, Methyl methacrylate, methyl methacrylate, butyl methacrylate, Hydroxyethyl acrylate, hydroxypropyl acrylate, Hydroxybutyl acrylate, hydroxyisobutyl acrylate, hydroxyethyl methacrylate, Hydroxypropyl methacrylate, hydroxyisobutyl methacrylate, Monomethyl maleate, dimethyl maleate, monoethyl maleate, Maleic acid diethyl ester, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylamide, methacrylamide, N-dimethylacrylamide, N-tert-butylacrylamide, acrylonitrile, methacrylonitrile, Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, Diethylaminoethyl acrylate, diethylaminoethyl methacrylate, the salts the latter monomers with carboxylic acids or mineral acids as well as the quaternized products. They are also suitable as Monomers acrylamidoglycolic acid, vinylsulfonic acid, allylsulfonic acid, Methallylsulfonic acid, styrene sulfonic acid, acrylic acid (3-sulfopropyl) ester, Methacrylic acid (3-sulfopropyl) ester and acrylamidomethylpropanesulfonic acid and phosphonic acid groups containing monomers such as vinyl phosphate, allyl phosphate and acrylamidomethyl propanephosphonic acid.

Weitere geeignete Verbindungen dieser Gruppe sind N-Vinylpyrrolidon, N-Vinylcaprolactam, N-Vinylimidazol, N-Vinyl-2-methylimidazolin, Diallylammoniumchlorid, Vinylacetat und Vinylpropionat. Es ist selbstverständlich auch möglich, Mischungen der genannten Monomere einzusetzen, beispielsweise zur Verbesserung der Haftung.Other suitable compounds of this group are N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinyl-2-methylimidazoline, Diallyl ammonium chloride, vinyl acetate and vinyl propionate. It is of course also possible to mix the use mentioned monomers, for example for improvement of liability.

Die Copolymeren sollten mindestens 20 Gew.-%, bevorzugt mindestens 50 Gew.-% N-Vinylamide einpolymerisiert, enthalten.The copolymers should be at least 20% by weight, preferably at least Polymerized 50% by weight of N-vinylamides.

Die Herstellung der Copolymerisate kann nach bekannten Verfahren, z.B. der Lösungs-, Fällungs-, Suspensions- oder Emulsionspolymerisation unter Verwendung von Verbindungen, die unter den Polymerisationsbedingungen Radikale bilden, erfolgen. Die Polymerisationstemperaturen liegen dabei üblicherweise in dem Bereich von 30 bis 200, vorzugsweise 40 bis 110°C. Geeignete Initiatoren sind beispielsweise Azo-, und Peroxyverbindungen sowie die üblichen Redoxinitiatorsysteme, wie Kombinationen aus Wasserstoffperoxyd und reduzierend wirkenden Verbindungen, z.B. Natriumsulfit, Natriumbisulfit, Natriumformaldehydsulfoxilat und Hydrazin. Diese Systeme können gegebenenfalls zusätzlich noch geringe Mengen eines Schwermetallsalzes enthalten.The copolymers can be prepared by known processes, e.g. solution, precipitation, suspension or emulsion polymerization using compounds operating under the polymerization conditions Form radicals, take place. The polymerization temperatures are usually in the range from 30 to 200, preferably 40 to 110 ° C. Suitable initiators are, for example, azo and peroxy compounds and the usual Redox initiator systems, such as combinations of hydrogen peroxide and reducing compounds, e.g. Sodium sulfite, Sodium bisulfite, sodium formaldehyde sulfoxylate and Hydrazine. If necessary, these systems can additionally contain small amounts of a heavy metal salt.

Die erfindungsgemäß einzusetzenden Homo- und Copolymeren besitzen im allgemeinen K-Werte von 7 bis 300, bevorzugt 10 bis 250. Die K-Werte können nach H. Fikentscher in wäßriger Lösung bei 25°C, bei Konzentrationen, die je nach K-Wert zwischen 0,1 % und 5 % liegen, gemessen werden.The homo- and copolymers to be used according to the invention have generally K values from 7 to 300, preferably 10 to 250. Die According to H. Fikentscher, K values can be measured in aqueous solution at 25 ° C, at concentrations between 0.1% and 5% depending on the K value lie, be measured.

Die oben beschriebenen Homo- bzw. Copolymerisate der allgemeinen Formel (I) werden durch Einwirkung von Säuren oder Basen dahingehend modifiziert, daß infolge dieser Behandlung die Formylgruppe aus dem einpolymerisierten N-Vinylformamid unter Bildung von Amin- bzw. Ammoniumgruppen abgespalten wird. Die Solvolysetemperaturen liegen üblicherweise im Bereich von 20 bis 100°C, vorzugsweise 70 bis 90°C. Geeignete Säuren sind beispielsweise Carbonsäuren wie Ameisensäure, Essigsäure oder Propionsäure, eine Sulfonsäure wie Benzolsulfonsäure oder Toluolsulfonsäure oder eine anorganische Säure wie Salzsäure, Schwefelsäure, Phosphorsäure oder Bromwasserstoffsäure.The homopolymers or copolymers of the general described above Formula (I) are done by the action of acids or bases modified that as a result of this treatment the formyl group from the polymerized N-vinylformamide to form is split off from amine or ammonium groups. The solvolysis temperatures are usually in the range from 20 to 100 ° C, preferably 70 to 90 ° C. Suitable acids are, for example Carboxylic acids such as formic acid, acetic acid or propionic acid, a Sulfonic acid such as benzenesulfonic acid or toluenesulfonic acid or an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid.

Als Basen eignen sich Natronlauge oder Kalilauge sowie Ammoniak, Amine und Erdalkalimetallbasen wie Kalziumhydroxid. Suitable bases are sodium hydroxide solution or potassium hydroxide solution and ammonia, Amines and alkaline earth metal bases such as calcium hydroxide.

Beispiele für die Herstellung der Homo- und Copolymerisate und die anschließende Solvolyse sind in DE-A-32 13 873 und DE-A-35 34 273 beschrieben.Examples for the production of homopolymers and copolymers and the subsequent solvolysis are in DE-A-32 13 873 and DE-A-35 34 273.

Zur Entsalzung der Polymerisate verwendet man die üblichen Methoden wie Ionenaustauscher, Elektrodialyse oder Ultrafiltration.The usual methods are used to desalt the polymers such as ion exchangers, electrodialysis or ultrafiltration.

Das erfindungsgemäße Verfahren ist insbesondere für die Behandlung von Eisen, Eisenlegierungen und chemisch vorbehandelten Untergrund, wie phosphatierten und ggf. mit Wasser bzw. Chromatlösung nachgespülten Metalloberflächen geeignet. Es eignet sich jedoch auch für die Oberflächenmodifizierung von Zink, Aluminium, Kupfer, Kobalt, Nickel und Mangan.The method according to the invention is particularly suitable for treatment of iron, iron alloys and chemically pretreated Substrate, such as phosphated and possibly with water or chromate solution rinsed metal surfaces suitable. It is suitable but also for the surface modification of zinc, aluminum, Copper, cobalt, nickel and manganese.

Die Aufbringung der wäßrigen Polymerlösung erfolgt, wie bereits oben erwähnt, zweckmäßigerweise durch Tauchen, Gießen oder Sprühen.The aqueous polymer solution is applied as already mentioned above, expediently by dipping, pouring or Spraying.

Für das erfindungsgemäße Verfahren können Polymerlösungen mit Feststoffgehalten zwischen 0,01 und 5, vorzugsweise zwischen 0,1 und 1 Gew.-% im Temperaturbereich zwischen 20 und 80°C eingesetzt werden.Polymer solutions can be used for the process according to the invention Solids content between 0.01 and 5, preferably between 0.1 and 1 wt .-% used in the temperature range between 20 and 80 ° C. become.

Die Modifizierung der Metalloberfläche durch das Aminogruppen enthaltende organische Polymer ließ sich durch Sekundärionen-Massenspektrometrie (TOF-SIMS) und Raster-Kraft-mikroskopie (RKM) nachweisen.The modification of the metal surface by the amino groups containing organic polymer could be determined by secondary ion mass spectrometry (TOF-SIMS) and atomic force microscopy (RKM) to prove.

Die mit dem erfindungsgemäßen Verfahren modifizierten Metall- oder chemisch vorbehandelten Metalloberflächen eignen sich prinzipiell für alle Zwecke, für die chemisch vorbehandelte Metalloberflächen geeignet sind. In Verbindung mit einer Lackierung, bewirken die Polymerschichten eine ungewöhnlich starke Verbesserung der Beständigkeit des Lackfilmes gegen Rostunterwanderung bei korrosiver Beanspruchung. Dieser Vorteil wird besonders bei der kathodischen Elektrotauchlackierung deutlich, weshalb das Verfahren für diese Lackierart besonders vorteilhaft angewendet wird. Praktische Anwendung findet das erfindungsgemäße Verfahren z.B. für Modifizierung von phosphatierten Autokarosserien.The modified metal or with the inventive method chemically pretreated metal surfaces are suitable in principle for all purposes, for chemically pretreated metal surfaces are suitable. In connection with a paint job, the polymer layers cause an unusually strong improvement the resistance of the paint film to rust infiltration with corrosive stress. This advantage becomes special with cathodic electrocoating, which is why the process is particularly advantageous for this type of painting is applied. The invention has practical application Procedure e.g. for modification of phosphated car bodies.

Die in den Beispielen genannten Teile und Prozente sind, soweit nicht anders angegeben, Gewichtsteile und Gewichtsprozente. The parts and percentages mentioned in the examples are so far not otherwise specified, parts by weight and percentages by weight.

Allgemeines Prüfverfahren:
190 x 105 x 0,75 mm große Prüfbleche wurden jeweils 1 Minute in wäßrige Polyvinylaminlösungen (K-Wert 30) getaucht. Die Konzentrationen der Polymerlösungen waren 0,01; 0,1; 1 und 2 %. Die Badtemperatur betrug jeweils 23° und 50°C, s. Tabelle. Nach dem Trocknen an Luft wurden die Bleche noch 5 Sekunden in vollentsalztes Wasser getaucht und erneut an Luft getrocknet.General test procedure:
Test sheets measuring 190 × 105 × 0.75 mm were immersed in aqueous polyvinylamine solutions (K value 30) for 1 minute each. The concentrations of the polymer solutions were 0.01; 0.1; 1 and 2 %. The bath temperature was 23 ° and 50 ° C, see. Table. After drying in air, the sheets were immersed in deionized water for a further 5 seconds and dried again in air.

Zur weiteren Prüfung der Wirkung wurden die vorbehandelten Prüfbleche mit einem Elektrotauchlack beschichtet.The pretreated test panels were used to further test the effect coated with an electrocoat.

Als Elektrotauchlack wurde eine Tauchbadlösung verwendet, wie sie in der DE-A-42 08 056 als Vergleichsbeispiel angegeben ist. An den als Kathode geschalteten Prüfblechen wurde bei Raumtemperatur in üblicher Weise der Lack abgeschieden und 25 Minuten bei 175°C eingebrannt. Bei Abscheidespannungen von 320 bis 380 V wurden Schichtdicken von 23 µm erzielt.An immersion bath solution, such as that used, was used as the electrodeposition paint is given in DE-A-42 08 056 as a comparative example. On the test sheets connected as cathode was at room temperature in the usual way the paint is deposited and 25 minutes at 175 ° C branded. With separation voltages from 320 to 380 V. Layer thicknesses of 23 microns achieved.

Als Maß für die Haftung der Lacke wurde die Unterrostung am Ritz bestimmt. Hierzu wurde auf den Stahlblechen ein 0,1 mm breiter Längsschnitt, auf den Blechen mit einer Phosphat-Konversionsschicht ein 0,1 mm breiter Kreuzschnitt in die Lackierung eingeritzt, der bis zum Blechuntergrund reichte.The rust at the Ritz was used as a measure of the adhesion of the paints certainly. For this purpose, a 0.1 mm wider was made on the steel sheets Longitudinal section, on the sheets with a phosphate conversion layer a 0.1 mm wide cross cut carved into the paintwork, that reached down to the sheet metal surface.

Die lackierten Stahlbleche wurde sodann 15 Tage im Salzsprühnebeltest (40°C, 5 %ige NaCl-Lösung: DIN 50 021) auf Korrosionsbeständigkeit geprüft. Die lackierten Stahlbleche mit Phosphat-Konversionsschicht wurden im salt-water-soak-test geprüft. Hierzu wurde das Prüfblech 10 Tage in eine auf 55°C aufgeheizte 5 %ige NaCl-Lösung eingetaucht.The painted steel sheets were then 15 days in the salt spray test (40 ° C, 5% NaCl solution: DIN 50 021) for corrosion resistance checked. The painted steel sheets with a phosphate conversion layer were tested in the salt water soak test. For this the test plate was heated for 10 days in a 5% solution heated to 55 ° C NaCl solution immersed.

In der Tabelle ist das maximale und durchschnittliche Ausmaß der Unterrostung (in Millimeter) an der Schnittstelle nach beiden Seiten hin angegeben.In the table is the maximum and average extent of Under rust (in millimeters) at the interface after both Sides indicated.

Die Referenzproben wurden analog nach den oben beschriebenen Verfahren elektrotauchlackiert und anschließend Korrosionstests unterzogen nur mit dem Unterschied, daß keine haftvermittelnde Schicht aufgebracht war. The reference samples were analogous to those described above Process electro-coated and then corrosion tests subjected only with the difference that no adhesion-promoting Layer was applied.

Beispiel 1example 1

Entfettetes Karosseriestahlblech (z.B. St 1405) wurde wie oben angegeben in wäßrige Polyvinylaminlösungen verschiedener Konzentration eingetaucht, nachbehandelt und elektrotauchlackiert.Degreased body steel sheet (e.g. St 1405) was as above specified in aqueous polyvinylamine solutions of various concentrations immersed, treated and electrocoated.

Beispiel 2Example 2

Beidseitig Manganmodifiziert-niedrigzink-phosphatiertes (Spritzverfahren) und anschließend mit Cr(VI)/Cr(III)-Lösung nachgespültes Stahlblech (BONDER® 26 60 OC) wurde wie oben angegeben in wäßrige Polyvinylaminlösungen verschiedener Konzentration eingetaucht und weiterverarbeitet.Manganese-modified, low-zinc-phosphated (spray process) on both sides and then rinsed with Cr (VI) / Cr (III) solution Steel sheet (BONDER® 26 60 OC) was given as above immersed in aqueous polyvinylamine solutions of various concentrations and processed.

Beispiel 3Example 3

Ein auf einer Seite verzinktes und auf der anderen Seite Manganmodifiziert-niedrigzink-phosphatiertes (Spritzverfahren) und anschließend mit Cr(VI)/Cr(III)-Lösung nachgespültes Stahlblech (BONDER® 26 W OM) wurde wie oben angegeben in wäßrige Polyvinylaminlösungen verschiedener Konzentration eingetaucht und weiterverarbeitet.One zinc-coated on one side and manganese-modified-low zinc-phosphated on the other side (Spray process) and then Steel sheet rinsed with Cr (VI) / Cr (III) solution (BONDER® 26 W OM) was, as stated above, in aqueous polyvinylamine solutions immersed in various concentrations and processed.

Beispiel 4Example 4

Ein beidseitig Manganmodifiziert-niedrigzink-phosphatiertes (Spritzverfahren) und anschließend mit Wasser nachgespültes Stahlblech (BONDER® 26 W OC) wurde wie oben angegeben in wäßrige Polyvinylaminlösungen verschiedener Konzentration eintaucht und weiterverarbeitet.A manganese-modified low-zinc-phosphated coating on both sides (Spray process) and then rinsed with water Steel sheet (BONDER® 26 W OC) was poured into aqueous as indicated above Immersed polyvinylamine solutions of various concentrations and processed further.

Die Prüfergebnisse sind in der Tabelle zusammengestellt.The test results are summarized in the table.

Bewertung der in den Beispielen erhaltenen Ergebnisse:
Der Korrosionstest zeigt an den Beispielen 1 bis 4 deutlich die Vorteile des erfindungsgemäßen Verfahrens im Vergleich zu den Referenzproben nach dem Stand der Technik.Evaluation of the results obtained in the examples:
The corrosion test clearly shows in Examples 1 to 4 the advantages of the method according to the invention compared to the reference samples according to the prior art.

Das Ausmaß der Unterrostung verringert sich durch die haftvermittelnde Polymerschicht bei den Proben mit Phosphat-Konversionsschicht um das zwei- bis dreifache. Bei dem beidseitig Manganmodifiziert-niedrigzink-phosphatierten (Spritzverfahren) und anschließend mit Cr(VI)/Cr(III)-Lösung nachgespülten Stahlblech verhindert das erfindungsgemäße Verfahren die Unterrostung vollständig. Auch beim entfetteten Karosseriestahlblech ist eine verringerte Unterrostung (Beispiel 1) festzustellen.The extent of the rust is reduced by the adhesion-promoting Polymer layer in the samples with a phosphate conversion layer by two to three times. In the case of the manganese-modified low-zinc phosphated on both sides (Spray process) and then Steel plate rinsed with Cr (VI) / Cr (III) solution The method according to the invention completely prevents rust formation. There is also one for degreased body steel sheet reduced rust formation (example 1).

Auch das gesamte Erscheinungsbild der Lackoberfläche zeigt durch das erfindungsgemäße Verfahren eine deutliche Verbesserung gegenüber dem Stand der Technik. Während die Lackflächen der Referenzproben starke Blasenbildung zeigen, ist die Lackoberfläche auf der mit wäßriger Polyvinylamin-Lösung modifizierten Metalloberfläche einwandfrei.The entire appearance of the paint surface also shows through the method according to the invention compared to a significant improvement the state of the art. While the lacquered surfaces of the reference samples show strong blistering, the paint surface is on the metal surface modified with aqueous polyvinylamine solution perfect.

Die besten Resultate wurden bei den Blechen mit Phosphat-Konversionsschichten mit einer 0,1 %igen Polyvinylaminlösung bei 50°C erhalten. Die geringste Unterwanderung auf blankem Stahl wurden bei Behandlung mit einer 1 %igen Polyvinylaminlösung (50°C Badtemperatur) erhalten.

Figure 00110001
The best results were obtained for the sheets with phosphate conversion layers with a 0.1% polyvinylamine solution at 50 ° C. The least infiltration on bare steel was obtained when treated with a 1% polyvinylamine solution (50 ° C bath temperature).
Figure 00110001

Claims (7)

  1. A method of modifying cleaned or chemically pretreated metal surfaces with aqueous solutions of organic polymers, wherein the cleaned or chemically pretreated metal surfaces are treated with an aqueous solution of organic polymers which contain amino groups.
  2. A method as claimed in claim 1, wherein the treatment with the aqueous solution of organic polymers which contain amino groups is effected by pouring, spraying or dipping.
  3. A method as claimed in any one of the preceding claims, wherein the metal surfaces are those of iron, ferro-alloys, zinc, aluminum, copper, cobalt, nickel or manganese.
  4. A method as claimed in any one of the preceding claims, wherein the chemically pretreated metal surfaces are metal surfaces with phosphate conversion coats.
  5. A method as claimed in any one of the preceding claims, wherein the organic polymers which contain amino groups are hydrolysis products of polymers comprising or consisting of units of the general formula (I)
    Figure 00140001
    in which R1 and R2 are identical to or different from one another and are hydrogen or alkyl of 1 to 6 carbon atoms.
  6. The use of the modified metal surfaces produced by a method as claimed in any one of the preceding claims for coating.
  7. The use of the modified metal surfaces produced by a method as claimed in any one of claims 1 to 5 for cathodic electrodeposition coating.
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Also Published As

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EP0672467A1 (en) 1995-09-20
DE59504710D1 (en) 1999-02-18
JPH0847666A (en) 1996-02-20
US5494535A (en) 1996-02-27
DE4409306A1 (en) 1995-09-21
ATE175365T1 (en) 1999-01-15

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