EP0126498B1 - Procédé pour la protection des métaux contre la corrosion - Google Patents

Procédé pour la protection des métaux contre la corrosion Download PDF

Info

Publication number
EP0126498B1
EP0126498B1 EP84200397A EP84200397A EP0126498B1 EP 0126498 B1 EP0126498 B1 EP 0126498B1 EP 84200397 A EP84200397 A EP 84200397A EP 84200397 A EP84200397 A EP 84200397A EP 0126498 B1 EP0126498 B1 EP 0126498B1
Authority
EP
European Patent Office
Prior art keywords
process according
resin
synthetic resin
cationic
corrosion
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
EP84200397A
Other languages
German (de)
English (en)
Other versions
EP0126498A1 (fr
Inventor
Peter Jörns
Werner Dr. Rausch
Gisela Rossmann
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.)
GEA Group AG
Continentale Parker Ste
Continentale Parker SA
Original Assignee
Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker SA
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 Metallgesellschaft AG, Continentale Parker Ste, Continentale Parker SA filed Critical Metallgesellschaft AG
Publication of EP0126498A1 publication Critical patent/EP0126498A1/fr
Application granted granted Critical
Publication of EP0126498B1 publication Critical patent/EP0126498B1/fr
Expired legal-status Critical Current

Links

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
    • B05D7/16—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 using synthetic lacquers or varnishes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment

Definitions

  • the invention relates to a method for corrosion protection of metals, in particular iron and steel, by applying a phosphate layer and impregnating the phosphate layer with organic synthetic resin.
  • a non-contiguous sealing layer of a hydrophobizing agent for. B. using organic materials, such as based on polyisocyanate modified resin condensation products (DE-AS 11 47820) or to seal with drying oils or low-viscosity paints (H. Fortmann «post-treatment process phosphated iron parts •, metalware industry and electroplating MSV No. 6 (1943), page 229).
  • organic materials such as based on polyisocyanate modified resin condensation products (DE-AS 11 47820) or to seal with drying oils or low-viscosity paints (H. Fortmann «post-treatment process phosphated iron parts •, metalware industry and electroplating MSV No. 6 (1943), page 229).
  • these agents could not prevail over the chromium-containing aftertreatment solutions for reasons of low quality.
  • many of these funds did not lead to useful results.
  • the pH of the solution used is usually in the alkaline range, which in the treatment of metal surfaces provided with conversion coatings can be associated with the disadvantage of partial delamination.
  • the object of the invention is to provide a method which does not have the disadvantages of the known methods and which provides surfaces with excellent corrosion protection and high abrasion resistance.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that a phosphate layer with a basis weight of at least 8 g / m 2 is first produced on the metal surface and at least electrolessly by means of an aqueous solution or dispersion of a cationic synthetic resin 8 g / m 2 synthetic resin applied and baked.
  • An advantageous development of the method according to the invention provides for a maximum of 40 g / m 2 of synthetic resin to be applied. Higher application weights practically no longer provide additional corrosion protection.
  • phosphate is the only anion in the acidic, aqueous phosphating solution.
  • other anions e.g. B. nitrate, nitrite, chloride, sulfate, chlorate, fluoride, complex fluoride, citrate, present.
  • the phosphating baths are particularly suitable for the process according to the invention, in which at least a considerable proportion of the iron pickled during the layer formation remains in solution as divalent iron.
  • the concentration of the phosphating baths is preferably chosen between 20 and 120 points.
  • the application temperature is usually in the range of 40 to 98 ° C.
  • the immersion process is preferred for layer formation because it allows the layer weight limit required in the invention to be maintained in a simpler manner than the spray process.
  • the phosphating times are usually 4 to 30 minutes.
  • the cationic synthetic resins used in the impregnation process according to the invention can be partially or fully neutralized with organic acids or phosphoric acid in the aqueous medium as an emulsion, dispersion and / or colloidal solution.
  • the solids content is preferably 5 to 25% by weight.
  • the cationic resins are selected from the group of polycondensation and polymerization resins and maintain their cationic function z.
  • B. by basic nitrogen-containing groups which form cations after addition of acid in an aqueous medium.
  • Cationic acrylate resins can be obtained, for example, by copolymerizing N, N-dimethylaminoethyl methacrylate.
  • Cationic resins can also be prepared by reacting Mannich bases of bisphenol A with epoxy resins. Modified epoxy resins which have been made acid-soluble by addition of an amine and in which crosslinking is made possible by addition of a half-capped diisocyanate during baking are particularly suitable for the process according to the invention.
  • the cationic synthetic resin from an aqueous solution or dispersion which additionally contains additives and modifiers known from the paint and color formulation, such as colorants, fillers and anti-corrosion pigments, soluble corrosion inhibitors, organic solvents and / or additives for an improved Film flow and to support the networking process when burning
  • paint formulations which are used for the cathodic electrocoating of metals.
  • they are successfully used as an aqueous medium containing cationic synthetic resin without the use of electric current.
  • the organic impregnation film is applied by wetting the phosphated surface with the aqueous solution or dispersion containing the cationic synthetic resin.
  • the wetting can be carried out by spraying on, pouring over, immersing and, if appropriate, subsequently spinning off excess liquid.
  • a further advantageous embodiment of the invention provides for the cationic resin to be applied by wetting it at least twice with brief drying and subsequent baking.
  • the intermediate drying should be carried out until the film has achieved sufficient mechanical strength.
  • the baking which concludes the application of the cationic synthetic resin, is usually carried out at object temperatures between 160 and 200 ° C. and holding times of 5 to 30 minutes.
  • An advantageous development of the invention consists in post-treating the phosphate layer with known Cr (VI) -containing aqueous passivating agents before the application of the cationic synthetic resin in order to further improve the corrosion protection. They can be formulated based on chromic acid, chromium chromate, alkali dichromate and the like.
  • the method according to the invention is particularly suitable for high-quality corrosion protection of Mass parts from the functional area.
  • Typical workpieces are screws, nuts, washers, springs, fasteners, brake parts and the like.
  • the protective value of the layers produced by the process according to the invention is usually significantly higher than that of chromated, electrolytically produced zinc and cadmium layers.
  • degreasing mentioned under 1. or the rust removal and descaling according to 3. can be omitted if the parts to be treated are free of grease or rust or scale.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (6)

1. Procédé pour la protection contre la corrosion de métaux, notamment de fer et d'acier, par application d'une couche de phosphate et imprégnation de la couche de phosphate avec une résine synthétique organique, caractérisé en ce que l'on réalise sur la surface du métal tout d'abord une couche de phosphate d'un poids par unité de surface d'au moins 8 g/m2 et on applique sans courant au moins 8 g/m2 de résine synthétique au moyen d'une solution aqueuse ou d'une dispersion d'une résine synthétique cationique, et on la cuit.
2. Procédé selon la revendication 1, caractérisé en ce que l'on applique et cuit au maximum 40 g/m2 de résine synthétique.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on applique la-résine synthétique cationique à partir d'une solution aqueuse ou d'une dispersion qui contient en plus des additifs et des produits de modification connus pour les laques et les peintures, tels que pigments colorants, pigments de charge et/ou pigments de protection contre la corrosion, des inhibiteurs solubles de corrosion, des solvants organiques et/ou des additifs pour améliorer la formation de films ainsi que pour aider l'opération de réticulation pendant la cuisson.
4. Procédé selon la revendication 1, 2 ou 3, caractérisé en ce que l'on applique la résine synthétique cationique en deux fois au moins avec séchage intermédiaire suivi d'une cuisson.
5. Procédé selon l'une ou plusieurs des revendications 1 à 4, caractérisé en ce que l'on traite la couche de phosphate avant application de la résine synthétique cationique avec un passivateur aqueux contenant du Cr(VI).
6. Procédé selon l'une ou plusieurs des revendications 1 à 5, caractérisé en ce qu'après cuisson de la résine synthétique cationique, on effectue un traitement complémentaire avec une huile de protection contre la corrosion.
EP84200397A 1983-04-26 1984-03-20 Procédé pour la protection des métaux contre la corrosion Expired EP0126498B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3315019 1983-04-26
DE19833315019 DE3315019A1 (de) 1983-04-26 1983-04-26 Verfahren zum korrosionsschutz von metallen

Publications (2)

Publication Number Publication Date
EP0126498A1 EP0126498A1 (fr) 1984-11-28
EP0126498B1 true EP0126498B1 (fr) 1987-06-16

Family

ID=6197351

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84200397A Expired EP0126498B1 (fr) 1983-04-26 1984-03-20 Procédé pour la protection des métaux contre la corrosion

Country Status (9)

Country Link
EP (1) EP0126498B1 (fr)
JP (1) JPS59205481A (fr)
AU (1) AU2713784A (fr)
BR (1) BR8401870A (fr)
DE (2) DE3315019A1 (fr)
ES (1) ES8506817A1 (fr)
GB (1) GB2138703B (fr)
PT (1) PT78408B (fr)
ZA (1) ZA843025B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4134301A1 (de) * 1991-10-17 1993-04-22 Herberts Gmbh Verfahren zur herstellung von mehrschichtueberzuegen mit kationischen fuellerschichten
DE4134290A1 (de) * 1991-10-17 1993-09-23 Herberts Gmbh Verfahren zur mehrschichtlackierung
US5693739A (en) * 1995-12-21 1997-12-02 Ppg Industries, Inc. Phenolic polymers from amino phenols and anhydride or epoxy polymers
FR2818572B1 (fr) † 2000-12-22 2003-03-14 Valeo Procede de fabrication d'une bague de synchronisation de boite de vitesses, notamment pour vehicule automobile

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH595459A5 (en) * 1973-03-19 1978-02-15 Zbrojovka Brno Np Polyphenylene oxide protective coatings for metals
DE2432593C3 (de) * 1974-07-06 1980-08-14 Nippon Paint Co., Ltd., Osaka (Japan) Verfahren zum Auftragen von Anstrichschichten auf leitfähige Werkstoffe
US4433015A (en) * 1982-04-07 1984-02-21 Parker Chemical Company Treatment of metal with derivative of poly-4-vinylphenol

Also Published As

Publication number Publication date
ZA843025B (en) 1985-06-26
EP0126498A1 (fr) 1984-11-28
AU2713784A (en) 1984-11-01
ES531122A0 (es) 1985-08-01
DE3315019A1 (de) 1984-10-31
PT78408B (fr) 1986-05-28
GB8410725D0 (en) 1984-05-31
ES8506817A1 (es) 1985-08-01
GB2138703A (en) 1984-10-31
BR8401870A (pt) 1984-11-27
GB2138703B (en) 1986-04-30
DE3464261D1 (en) 1987-07-23
PT78408A (fr) 1984-05-01
JPS59205481A (ja) 1984-11-21

Similar Documents

Publication Publication Date Title
EP0091166B1 (fr) Procédé pour traiter de surfaces métalliques
DE69405530T2 (de) Verfahren und Zusammensetzung zur Metallbehandlung
DE69934780T2 (de) Oberflächenbehandeltes stahlblech mit hervorragendem korrosionwiderstand
EP0187917B1 (fr) Procédé pour la protection anticorrosive de couches de résine déposées autophorétiquement sur surfaces métalliques
EP0356855B1 (fr) Prétraitement de surfaces en aluminium ou alliages d'aluminium à revêtir avec des matériaux organiques sans utilisation de chrome
DE3146265A1 (de) Nachbehandlung von chemischen umwandlungsueberzuegen
WO2008135478A2 (fr) Prétraitement de métallisation de surfaces de zinc
EP2475468A1 (fr) Procédé en deux étapes pour le traitement anticorrosion de surfaces métalliques
EP0149720B1 (fr) Procédé de post passivation de surfaces métalliques phosphatées, utilisant des solutions contenant des cations de titane et/ou manganèse et/ou cobalt et/ou nickel et/ou cuivre
EP1692325A1 (fr) Traitement de conversion en deux etapes
DE2100021A1 (de) Verfahren zum Aufbringen von Phos phatschichten auf Stahl, Eisen und Zinkoberflachen
EP0410497B1 (fr) Procédé pour le rinçage passif de couches de phosphates
DE1521880B1 (de) Verfahren zur Behandlung von chemisch aufgebrachten UEberzuegen auf Metallen mit chromhaltigen Loesungen
EP0492713A1 (fr) Procédé de post-rinçage de couches de conversion
EP0111246B1 (fr) Procédé pour phosphater des objets métalliques zingués électrolytiquement
EP0713539A1 (fr) Procede de phosphatage d'un feuillard d'acier galvanise une face
DE10030462A1 (de) Haftvermittler in Konversionslösungen
EP0126498B1 (fr) Procédé pour la protection des métaux contre la corrosion
DE2218899C2 (de) Wäßrige, chromatablagernde Zusammensetzung und deren Verwendung
DE102009017702B4 (de) Verfahren zur Bildung von Korrosionsschutzschichten auf Metalloberflächen
WO1999014397A1 (fr) Procede de phosphatation d'un feuillard d'acier
EP0154384B1 (fr) Procédé de prétraitement de surfaces en zinc pour le laquage
DE68906651T2 (de) Zusammensetzung und verfahren zur behandlung von metalloberflaechen.
DE943152C (de) Verfahren zur Herstellung von Korrosionsschutzschichten auf Metallen, insbesondere Eisen und Stahl
DE9310549U1 (de) Harzverguetete phosphatierte metalloberflaeche

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE DE FR IT NL SE

17P Request for examination filed

Effective date: 19850420

17Q First examination report despatched

Effective date: 19860502

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR IT NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19870616

REF Corresponds to:

Ref document number: 3464261

Country of ref document: DE

Date of ref document: 19870723

ET Fr: translation filed
ITF It: translation for a ep patent filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19890331

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19901001

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19910412

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19911217

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19920115

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19921201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19930321

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19931130

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 84200397.2

Effective date: 19931008