EP0672467B1 - Procédé pour la modification de surfaces métalliques - Google Patents

Procédé pour la modification de surfaces métalliques 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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Prior art keywords
sample
metal surfaces
acid
immersed
cleaned
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EP95103462A
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German (de)
English (en)
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EP0672467A1 (fr
Inventor
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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Chemically Coating (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (7)

  1. Procédé pour modifier des surfaces métalliques nettoyées ou qui ont subi un traitement chimique préalable, à l'aide de solutions aqueuses de polymères organiques, caractérisé par le fait que l'on traite les surfaces métalliques nettoyées ou ayant subi le traitement chimique préalable par une solution aqueuse de polymères organiques contenant des groupes amino.
  2. Procédé selon la revendication 1, caractérisé par le fait que le traitement par une solution aqueuse de polymères organiques contenant des groupes amino est réalisé par coulée, pulvérisation ou immersion.
  3. Procédé selon une des revendications qui précèdent, caractérisé par le fait que les surfaces métalliques sont des surfaces de fer, d'alliages de fer, de zinc, d'aluminium, de cuivre, de cobalt, de nickel ou de manganèse.
  4. Procédé selon une des revendications qui précèdent, caractérisé par le fait que les surfaces métalliques qui ont subi un traitement chimique préalable sont des surfaces métalliques qui portent des couches de conversion phosphatées.
  5. Procédé selon une des revendications qui précèdent, caractérisé par le fait que les polymères organiques contenant des groupes amino sont des produits d'hydrolyse de polymères contenant des motifs de formule générale I
    Figure 00160001
    ou qui consistent en tels motifs, dans lesquels R1 et R2, ayant des significations identiques ou différentes, représentent H ou des groupes alkyle en C1-C6.
  6. Utilisation de surfaces métalliques modifiées, obtenues par un procédé selon l'une des revendications qui précèdent, pour l'application de revêtements.
  7. Utilisation de surfaces métalliques modifiées, obtenues par un procédé selon une des revendications 1 à 5, pour l'application de revêtements par électrodéposition cathodique en immersion.
EP95103462A 1994-03-18 1995-03-10 Procédé pour la modification de surfaces métalliques Expired - Lifetime EP0672467B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4409306 1994-03-18
DE4409306A DE4409306A1 (de) 1994-03-18 1994-03-18 Verfahren zur Modifizierung von Metalloberflächen

Publications (2)

Publication Number Publication Date
EP0672467A1 EP0672467A1 (fr) 1995-09-20
EP0672467B1 true EP0672467B1 (fr) 1999-01-07

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EP95103462A Expired - Lifetime EP0672467B1 (fr) 1994-03-18 1995-03-10 Procédé pour la modification de surfaces métalliques

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US (1) US5494535A (fr)
EP (1) EP0672467B1 (fr)
JP (1) JPH0847666A (fr)
AT (1) ATE175365T1 (fr)
DE (2) DE4409306A1 (fr)

Families Citing this family (13)

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JP4043551B2 (ja) * 1997-05-23 2008-02-06 栗田工業株式会社 スケール防止剤及びスケール防止方法
DE10013828A1 (de) * 1999-04-01 2000-10-05 Basf Ag Vorrichtung, aufweisend eine gegen unerwünschte Abscheidung von Polymer geschützte metallische Oberfläche
DE19961411A1 (de) * 1999-12-17 2001-06-21 Chemetall Gmbh Verfahren zur Herstellung von beschichteten Metalloberflächen und deren Verwendung
US6743302B2 (en) 2000-01-28 2004-06-01 Henkel Corporation Dry-in-place zinc phosphating compositions including adhesion-promoting polymers
DE10164671A1 (de) * 2001-12-27 2003-07-10 Basf Ag Derivate von Polymeren für die Metallbehandlung
DE10163892A1 (de) * 2001-12-27 2003-07-17 Basf Ag Derivate von Polymeren für die Metallbehandlung
DE10310972A1 (de) 2003-03-13 2004-09-23 Basf Ag Stickstoffhaltige Polymere für die Metalloberflächenbehandlung
DE102005023728A1 (de) * 2005-05-23 2006-11-30 Basf Coatings Ag Lackschichtbildendes Korrosionsschutzmittel und Verfahren zu dessen stromfreier Applikation
DE102006053291A1 (de) * 2006-11-13 2008-05-15 Basf Coatings Ag Lackschichtbildendes Korrosionsschutzmittel mit guter Haftung und Verfahren zu dessen stromfreier Applikation
DE102007012406A1 (de) * 2007-03-15 2008-09-18 Basf Coatings Ag Verfahren zur Korrosionsschutzausrüstung metallischer Substrate
DE102008053517A1 (de) * 2008-10-28 2010-04-29 Henkel Ag & Co. Kgaa Lackhaftung durch Polyvinylamine in sauren wässrigen polymerhaltigen Korrosionsschutzmitteln
DE102009007632A1 (de) 2009-02-05 2010-08-12 Basf Coatings Ag Beschichtungsmittel für korrosionsstabile Lackierungen
CN105102687A (zh) * 2013-04-02 2015-11-25 株式会社Adeka 电镀铜浴用添加剂、含该添加剂的电镀铜浴及使用该电镀铜浴的电镀铜方法

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Also Published As

Publication number Publication date
US5494535A (en) 1996-02-27
DE4409306A1 (de) 1995-09-21
DE59504710D1 (de) 1999-02-18
JPH0847666A (ja) 1996-02-20
ATE175365T1 (de) 1999-01-15
EP0672467A1 (fr) 1995-09-20

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