EP0187917B1 - Procédé pour la protection anticorrosive de couches de résine déposées autophorétiquement sur surfaces métalliques - Google Patents

Procédé pour la protection anticorrosive de couches de résine déposées autophorétiquement sur surfaces métalliques Download PDF

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Publication number
EP0187917B1
EP0187917B1 EP85114639A EP85114639A EP0187917B1 EP 0187917 B1 EP0187917 B1 EP 0187917B1 EP 85114639 A EP85114639 A EP 85114639A EP 85114639 A EP85114639 A EP 85114639A EP 0187917 B1 EP0187917 B1 EP 0187917B1
Authority
EP
European Patent Office
Prior art keywords
metal
chromium
salts
water
metal surfaces
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.)
Expired
Application number
EP85114639A
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German (de)
English (en)
Other versions
EP0187917A1 (fr
Inventor
Lutz Schellenberg
Matthias Hamacher
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.)
Gerhard Collardin GmbH
Original Assignee
Gerhard Collardin GmbH
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.)
Filing date
Publication date
Application filed by Gerhard Collardin GmbH filed Critical Gerhard Collardin GmbH
Priority to AT85114639T priority Critical patent/ATE39502T1/de
Publication of EP0187917A1 publication Critical patent/EP0187917A1/fr
Application granted granted Critical
Publication of EP0187917B1 publication Critical patent/EP0187917B1/fr
Expired legal-status Critical Current

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Classifications

    • 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
    • B05D7/142—Auto-deposited coatings, i.e. autophoretic coatings
    • B05D7/144—After-treatment of auto-deposited coatings

Definitions

  • the invention relates to a method with which the corrosion protection can be significantly improved autophoretically on metal surfaces of resin layers compared to previously known methods.
  • barium, strontium, zinc or lead compounds are used as corrosion protection pigments, the chromates of the metals mentioned being preferably used. Without exception, these chromates are poorly soluble in water.
  • the inorganic pigments mentioned which are to ensure improved corrosion protection, directly to the coating bath.
  • the autophoretic coating process is based on the fact that the acidic aqueous resin dispersion stains the metal surface to be coated and metal ions of the metal layer to be coated thereby dissolve. These positive charge carriers coagulate the stabilized resin dispersion in the vicinity of the metal surface, which causes a homogeneous coating of the metal surface with the organic resin. Due to the low pH value of this coating process (between 1.5 and 4.0), the corrosion protection pigments mentioned, which have only a low solubility in water, are more or less quickly converted into a soluble form.
  • the object of the invention was to overcome the disadvantage of using such anti-corrosion pigments in autophoretic coating baths. Surprisingly, it was found that stable organic layers with excellent corrosion protection properties can be obtained on metal surfaces if the metal surfaces are immersed in an aqueous metal salt solution after the actual coating reaction before the organic resin film dries and the metal salts remaining in the organic film are subsequently dried Immersed in an aqueous, hexavalent and possibly also trivalent chromium-containing rinsing solution converted into chromates and then the chromate-containing coating of the metal surface dries and burns.
  • metals such as aluminum, zinc, iron, nickel, tin, lead and chromium or their alloys can be used as metal surfaces for the process according to the invention. This also includes metal surfaces that are coated with one of the metals mentioned or one of their alloys.
  • the metal surfaces mentioned are mechanically and / or chemically, e.g. by treatment with an alkaline cleaning solution, cleaned and thus prepared for the process step of autophoretic coating.
  • the cleaned metal surfaces are autophoretically coated by treatment with an aqueous acidic dispersion of an organic resin.
  • the organic resins that can be used for this coating step are generally known and commercially available.
  • dispersions of styrene-butadiene copolymers, acrylic acid copolymers, acrylonitrile-butadiene copolymers, ethylene-vinyl acetate copolymers, polyethylene homopolymeric or other resins known from the prior art can be used.
  • the metal surfaces autophoretically coated with an organic resin are rinsed with water before further treatment.
  • the metal surfaces coated with an organic resin and not yet dried are then brought into contact with an aqueous solution of a readily water-soluble salt of a metal from the group of strontium, barium, lead, nickel, copper and zinc.
  • a readily water-soluble salt of a metal from the group of strontium, barium, lead, nickel, copper and zinc.
  • Lead or nickel salts are preferably used.
  • the anions of the salts which can be used according to the invention are subject, on the one hand, to the requirement that salts with the respective metal cations be readily soluble in water. In addition, they must not belong to the group of those anions which in any way have a detrimental effect on the result of the process according to the invention.
  • salts of hydrohalic acids or sulfuric acid are not suitable according to the invention, since the anions, for example CI and SO 4 2 , are known to have a corrosive effect on metal surfaces and their solutions therefore at least partially compensate for the purpose of improving corrosion protection on metal surfaces.
  • Salts of the metals mentioned with anions of organic carboxylic acids have proven particularly useful for use in the process according to the invention.
  • the ethanates (acetates), propanates (propionates) or salts of higher carboxylic acids or dicarboxylic acids can be used.
  • the ethanates (acetates) of the metals mentioned are preferred, since when the deposited coating is baked in the presence of Cr (VI) ions it can be assumed that the anions decompose to C0 2 and H 2 0. These decomposition products do not negatively affect the corrosion protection of the metal surfaces.
  • the content of metal salts in the aqueous solutions with which the autophoretically coated metal surfaces are treated according to the invention can vary within wide limits. It is between 1 and 10 g of metal ion per liter of application solution, preferably 2.5 to 7 g of metal ion per liter of application solution.
  • the aqueous solutions When treating the metal surfaces, the aqueous solutions have a pH in the range from 4.5 to 8.5. If necessary, using the acid, the salt of which is used to improve corrosion protection, the pH can be lowered within the range mentioned. Solutions containing lead or nickel ethanate are adjusted to a pH in the range from 4.9 to 5.3 using ethanoic acid (acetic acid).
  • the metal surfaces prepared as described above and coated with an organic resin are brought into contact with the salt solutions mentioned according to methods known per se. This can consist in immersing the coated metal plates in the metal salt solutions, spraying them with these solutions or treating them in combined immersion / spray processes.
  • the treatment time is 30 to 120 sec, preferably 90 sec.
  • the salt solutions have temperatures in the range from 4 to 50 ° C; treatment at 20 ° C. is preferred.
  • the salts are in the still soft organic. African layer installed. However, they are accessible to further chemical reactions and are treated according to the invention in a subsequent step with an aqueous solution containing chromium, the respective organic metal salts being converted into the corresponding chromates.
  • the aqueous solution required for the step of converting the water-soluble metal salts into the corresponding chromates contains water-soluble hexavalent chromium compounds.
  • examples of such compounds are chromic acid, potassium dichromate, magnesium dichromate, potassium chromate and sodium chromate.
  • any chromium-containing compound can be used which forms chromium (VI) ions in an acidic aqueous medium.
  • Preferred sources of chromium (VI) are dichromates, for example calcium dichromate.
  • Such solutions can also be prepared by mixing aqueous chromic acid solutions with appropriate salts, e.g. Calcium carbonate, added.
  • Solutions that contain trivalent chromium in addition to hexavalent are preferred. Such solutions can be produced according to the prior art by partially reducing Cr (VI) -containing solutions with suitable reducing agents. A known possibility is e.g. in adding formaldehyde to chromic acid solutions and thereby reducing some of the Cr (VI) to Cr (III).
  • the molar ratio of Cr (III) to Cr (VI) in the solutions mentioned is in the range from 0.3 to 3: 1.
  • the solutions contain a total of 1 to 20 g of chromium per liter of application solution, preferably 5 to 15 g of chromium per liter of application solution.
  • the conversion of the metal salts introduced into the organic resin layer in the first process step into the corresponding chromates also takes place according to methods known from the prior art.
  • the metal surfaces can either be immersed in the chromium-containing aqueous solutions or sprayed with them, or they can also be treated by combined immersion / spray processes.
  • the treatment time is in the range from 30 to 120, preferably 90 seconds, at temperatures from 4 to 50 ° C., preferably 20 ° C.
  • Metal autophoretically coated with an organic resin and additionally protected against corrosion with a metal chromate Surfaces are then dried in a manner known per se, elevated temperatures of from 90 to 150 ° C., preferably of 110 ° C., being used where appropriate. The temperature used in each case depends on the organic resin used for the coating. A completely closed organic resin surface is formed which, due to its metal chromate content, protects the metal surface against corrosion much better than non-post-treated or only post-treated metal surfaces with chromic acid.
  • test sheets were immersed in the metal salt solution for 90 seconds at 20 ° C. - see Table 1 - and then for 90 seconds at 20 ° C. in a solution containing 6.15 g / l Chromium (III) and 10.9 g / I chromium (VI) contained, rinsed. Then the test panels were 30 min. dried at 110 ° C in the oven.
  • the corrosion protection according to DIN 5316 and VW test specification No. 3.17.1 from January 6th, 1981 was tested on the test sheets produced in this way.
  • the test panels were loaded for 240 hours and 480 hours, respectively, and assessed after a recovery time of 1 hour.
  • the test sheets were shot with steel shot, the salt spray test was carried out in accordance with DIN 50021, the test sheets were shot again with steel shot after a rest period of 1 hour, and the number and size of the breakthroughs were evaluated.
  • Table 2 contains the assessment of the test panels.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)
  • Detergent Compositions (AREA)

Claims (14)

1. Procédé pour améliorer la protection contre la corrosion des couches résineuses déposées par autophorèse sur des surfaces métalliques, dans lequel les surfaces métalliques nettoyées par des méthodes connues en elles-mêmes, enduites par autophorèse d'une résine organique quelconque et éventuellement rincées à l'eau,
a) sont mises en contact avec une solution aqueuse d'un sel à bonne solubilité dans l'eau d'un métal du groupe strontium, baryum, plomb, nickel, cuivre et zinc à une valeur de pH dans l'intervalle de 4,5 à 8,5,
b) on convertit les sels métalliques restés dans le film organique, par traitement avec une solution aqueuse contenant du chrome hexavalent et éventuellement aussi du trivalent, en des chromates et
c) on sèche d'une manière connue en elle-même la couche organique contenant les chromates métalliques et/ou on la cuît à une température plus élevée.
2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise des sels de plomb ou de nickel à une valeur de pH dans l'intervalle de 4,9 à 5,3.
3. Procédé suivant les revendications 1 et 2, caractérisé en ce qu'on utilise des sels d'acides carboxyliques ou d'acides dicarboxyliques organiques.
4. Procédé suivant la revendication 3, caractérisé en ce qu'on utilise des éthanoates (acétates).
5. Procédé suivant les revendications 1 à 4, caractérisé en ce qu'on règle la teneur en métal à une valeur de 1 à 10 g d'ions métalliques par litre de solution d'application, de préférence à une valeur de 2,5 à 7 g d'ions métalliques par litre de solution d'application.
6. Procédé suivant les revendications 1 à 5, caractérisé en ce qu'on utilise pour la conversion des sels métalliques en les chromates correspondants des solutions aqueuses qui contiennent un composé de chrome (VI) soluble dans l'eau.
7. Procédé selon les revendications 1 à 6, caractérisé en ce qu'en tant de composé de chrome (VI) soluble dans l'eau on utilise un composé du groupe acide chromique, bichromate de potassium, bichromate de magnésium, bichromate de calcium, chromate de sodium et chromate de potassium.
8. Procédé selon les revendications 1 à 7, caractérisé en ce qu'en tant que composé de chrome (VI) soluble dans l'eau on utilise des bichromates, de préférence du bichromate de calcium.
9. Procédé selon les revendications 1 à 8, caractérisé en ce qu'on utilise du bichromate de calcium préparé à partir de solutions aqueuses d'acide chromique et de carbonate de calcium.
10. Procédé selon les revendications 1 à 5, caractérisé en ce que pour la conversion des sels métalliques en les bichromates correspondants on utilise des solutions aqueuses contenant du chrome (VI) et du chrome (III).
11. Procédé suivant la revendication 10, caractérisé en ce qu'on utilise des solutions dans lesquelles le rapport molaire Cr (III) : Cr (VI) se situe dans l'intervalle de 0,3 à 3:1.
12. Procédé selon les revendications 1 à 11, caractérisé en ce qu'on utilise 1 à 20 g de chrome par litre de solution d'application, de préférence 5 à 15 g de chrome par litre de solution d'application.
13. Procédé selon les revendications 1 à 12, caractérisé en ce que la durée du traitement des surfaces métalliques enduites par autophorèse avec les solutions de sel métallique et de chrome se situe dans l'intervalle de 30 à 120 secondes, de préférence pendant 90 secondes.
14. Procédé selon les revendications 1 à 13, caractérisé en ce que les solutions aqueuses contenant un sel métallique ou un composé de chrome ont une température dans l'intervalle de 4 à 50 °C, de préférence une température de 20 °C.
EP85114639A 1985-01-09 1985-11-18 Procédé pour la protection anticorrosive de couches de résine déposées autophorétiquement sur surfaces métalliques Expired EP0187917B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85114639T ATE39502T1 (de) 1985-01-09 1985-11-18 Verfahren zur verbesserung des korrosionsschutzes autophoretisch abgeschiedener harzschichten auf metalloberflaechen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3500443 1985-01-09
DE19853500443 DE3500443A1 (de) 1985-01-09 1985-01-09 Verfahren zur verbesserung des korrosionsschutzes autophoretisch abgeschiedener harzschichten auf metalloberflaechen

Publications (2)

Publication Number Publication Date
EP0187917A1 EP0187917A1 (fr) 1986-07-23
EP0187917B1 true EP0187917B1 (fr) 1988-12-28

Family

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Family Applications (1)

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EP85114639A Expired EP0187917B1 (fr) 1985-01-09 1985-11-18 Procédé pour la protection anticorrosive de couches de résine déposées autophorétiquement sur surfaces métalliques

Country Status (8)

Country Link
US (1) US4636264A (fr)
EP (1) EP0187917B1 (fr)
JP (1) JPS61174973A (fr)
CN (1) CN1008527B (fr)
AT (1) ATE39502T1 (fr)
BR (1) BR8600052A (fr)
CA (1) CA1245918A (fr)
DE (2) DE3500443A1 (fr)

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DE3442985A1 (de) * 1984-11-26 1986-05-28 Henkel KGaA, 4000 Düsseldorf Verfahren zur verbesserung des korrosionsschutzes von autophoretisch abgeschiedenen harzueberzuegen auf metalloberflaechen
DE3909694A1 (de) * 1988-03-30 1989-10-12 Nihon Parkerizing Erzeugung schwarzer ueberzuege auf harten oberflaechen
FR2685352A1 (fr) * 1991-12-24 1993-06-25 Pont A Mousson Revetement multicouche, avec son procede d'obtention et son application.
US5470613A (en) * 1992-01-21 1995-11-28 Betz Laboratories, Inc. Composition and method of forming a black no-rinse conversion coating on metal surfaces
US5441773A (en) * 1992-01-21 1995-08-15 Betz Laboratories, Inc. Composition and method of forming a black no-rinse conversion coating on metal surfaces
US5385758A (en) * 1992-12-30 1995-01-31 Henkel Corporation Method for applying autodeposition coating
US5372853A (en) * 1993-08-05 1994-12-13 Henkel Corporation Treatment to improve corrosion resistance of autodeposited coatings of metallic surfaces
US5667845A (en) * 1993-08-05 1997-09-16 Henkel Corporation Treatment to improve corrosion resistance of autodeposited coatings on metallic surfaces
JP3515183B2 (ja) * 1994-08-30 2004-04-05 臼井国際産業株式会社 金属管における耐食性樹脂被覆構造
US5704995A (en) * 1996-07-16 1998-01-06 Globe Motors, A Division Of Labinal Components And Systems, Inc. Method for forming a black, adherent coating on a metal substrate
US5786030A (en) * 1996-11-12 1998-07-28 Henkel Corporation Spotting resistant gloss enhancement of autodeposition coating
US6410092B1 (en) 1999-05-21 2002-06-25 Henkel Corporation Autodeposition post-bath rinse process
MXPA01012770A (es) * 1999-05-26 2002-07-22 Henkel Corp Revestimientos de autodeposicion y procesos para los mismos.
WO2001061894A2 (fr) * 2000-02-18 2001-08-23 Penguinradio, Inc. Dispositif audio cable compatible avec l'internet
TW570842B (en) 2000-11-22 2004-01-11 Nihon Parkerizing Protective reaction rinse for autodeposition coatings
US6989411B2 (en) * 2001-11-14 2006-01-24 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Epoxy dispersions for use in coatings
WO2004007443A2 (fr) * 2002-07-15 2004-01-22 Henkel Kommanditgesellschaft Auf Aktien Films resistant a la corrosion a base d'emulsions epoxy modifiees par monomere insature en ethylene
US7388044B2 (en) * 2002-07-15 2008-06-17 Henkel Kommanditgesellschaft Auf Aktien Coatings with enhanced water-barrier and anti-corrosive properties
DE102009029334A1 (de) * 2009-09-10 2011-03-24 Henkel Ag & Co. Kgaa Zweistufiges Verfahren zur korrosionsschützenden Behandlung von Metalloberflächen
US9228109B2 (en) 2010-12-20 2016-01-05 Henkel Ag & Co. Kgaa Glossy improved appearance auto-deposition coating, and methods of applying same
WO2012087813A2 (fr) 2010-12-20 2012-06-28 Henkel Ag & Co. Kgaa Revêtement brillant applicable par auto-déposition présentant un aspect amélioré et ses procédés d'application
US10323314B2 (en) 2011-06-17 2019-06-18 Henkel Ag & Co. Kgaa Single bath autodeposition coating for combination metal substrates and methods therefor
US9115442B2 (en) 2013-03-15 2015-08-25 Henkel Ag & Co. Kgaa Electrodeposition of an autodepositable polymer
WO2017117169A1 (fr) 2015-12-31 2017-07-06 Henkel Ag & Co. Kgaa Revêtements à autodépôt à faible cuisson

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Also Published As

Publication number Publication date
CN86100013A (zh) 1986-07-09
EP0187917A1 (fr) 1986-07-23
US4636264A (en) 1987-01-13
BR8600052A (pt) 1986-09-23
CN1008527B (zh) 1990-06-27
CA1245918A (fr) 1988-12-06
ATE39502T1 (de) 1989-01-15
DE3567035D1 (en) 1989-02-02
DE3500443A1 (de) 1986-09-11
JPS61174973A (ja) 1986-08-06

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