EP0154384B1 - Procédé de prétraitement de surfaces en zinc pour le laquage - Google Patents

Procédé de prétraitement de surfaces en zinc pour le laquage Download PDF

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Publication number
EP0154384B1
EP0154384B1 EP19850200318 EP85200318A EP0154384B1 EP 0154384 B1 EP0154384 B1 EP 0154384B1 EP 19850200318 EP19850200318 EP 19850200318 EP 85200318 A EP85200318 A EP 85200318A EP 0154384 B1 EP0154384 B1 EP 0154384B1
Authority
EP
European Patent Office
Prior art keywords
solution
metal
process according
degreased
cleaned
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
EP19850200318
Other languages
German (de)
English (en)
Other versions
EP0154384A3 (en
EP0154384A2 (fr
Inventor
Patrick Ajenherc
Gilles Garnier
Guy Lorin
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 EP0154384A2 publication Critical patent/EP0154384A2/fr
Publication of EP0154384A3 publication Critical patent/EP0154384A3/de
Application granted granted Critical
Publication of EP0154384B1 publication Critical patent/EP0154384B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/20—Other heavy metals

Definitions

  • the invention relates to a method for preparing metal surfaces made of zinc or zinc alloys for the subsequent application of paint, lacquer and the like. By means of alkaline cleaning and passivation through chemical conversion coatings.
  • aqueous solutions to form conversion coatings which contain alkali, generally sodium hydroxide, cations of at least one metal other than alkali ions, preferably iron, cobalt and / or nickel, and at least one Contain complexing agents.
  • the amount of the complexing agent should be sufficient to keep the aforementioned cations in solution in the alkaline medium from which they would precipitate as metal hydroxide without the complexing agent.
  • the most frequently used complexing agents for this are sodium gluconate and sodium glucoheptonate.
  • the solutions for producing the chemical conversion coating are usually applied by spraying at a temperature between 40 and 70 ° C. for a period of about 3 to 15 seconds.
  • aqueous alkaline solutions for the formation of conversion coatings is associated with significant progress in terms of paint adhesion and corrosion resistance after painting, especially for strip and sheet metal.
  • Industrial experience has also confirmed that it is interesting to subject the metal surface to a subsequent treatment with an aqueous acidic solution in accordance with FR-PS-1 487 183 after the formation of a conversion coating in an alkaline medium and water rinsing.
  • Such solutions contain 0.001 to 0.25% by weight of chromium (III), 0.01 to 0.06% by weight of fluoride and 0.02 to 0.1% by weight of zinc. They are used in spraying or dipping for 2 to 10 seconds at a temperature between 40 and 70 ° C. The surfaces are then dried immediately so that they can then be painted or painted.
  • the object of the present invention is to provide a method which avoids the disadvantages of the known, in particular the aforementioned methods, and which is associated with an improvement in the adhesion of paint, paint and the like and the corrosion resistance.
  • the type and amount of alkaline Cleaning agents are preferably chosen such that the pH of the solution is 11.5 to 12.5.
  • the alkaline cleaning agents can be hydroxides, phosphates, carbonates and borates of alkali metals with the exception of silicate. These components are usually used in a concentration of 3 to 150 g / l, preferably 7 to 9 g / l.
  • the surfactants can in principle be anion-active, non-ionic, cation-active or amphoteric. They must be compatible in the alkaline medium and under the conditions of use of the solution. Your choice depends essentially on the pH of the cleaning and degreasing agent, the conditions of use, i. H. Dip or spray application, and economic considerations. For solutions used in the spray process, nonionic surfactants are preferred. Their concentration should be between 0.1 and 5 g / l, preferably about 1 g / l. Such surfactants can be used alone or in a mixture.
  • the metal ions other than alkali ions can be selected from those mentioned in French Patent 1,411,272. These are in particular aluminum, antimony, silver, cadmium, cerium, chromium, cobalt, tin, iron (11 or III-valent), magnesium, manganese, molybdenum, nickel, titanium and tungsten. Cobalt, iron and nickel ions are preferred, especially nickel.
  • the anion assigned to the cation for introduction should be compatible with the solution and should not have any adverse effect. For this reason, nitrate is preferably used to introduce the metal ions other than alkali ions.
  • the concentration of the metal cations other than alkali ions in the solution depends on the concentration of the alkaline cleaning agent. The higher it is, the higher the concentration of cations should be.
  • the concentration of cations other than alkali ions can be between 50 and 5000 mg / l, preferably between 100 and 1000 mg / l. With a concentration of the alkaline-reacting cleaning agent of approx. 10 g / l and a pH of the order of 12, the preferred range of the metal cations is 500 to 700 mg / l.
  • the improvement can practically not be greater than that which is usually obtained with the preferred concentration of 500 to 700 mg / l. Due to the high pH, the conditions of use and the high content of cations other than alkali ions, the solution is not entirely sludge-free, which is not harmful, however, if the amount of sludge is small, i.e. is in the order of 2 to 3% by volume, based on the entire solution.
  • the complexing agents used in the cleaning and degreasing solution can be the same as those described in FR-PS-1 411 272.
  • it can be condensed phosphates, dicarboxylic acids, hydroxy carboxylic acids, benzene carboxylic acids, hydroxy aldehydes and amines.
  • the best results in terms of degreasing the metal surface and complexing the metal ions can be achieved with sodium gluconate, sodium glucoheptonate, sorbitol and sodium ethylenediaminotetraacetate.
  • the concentration of complexing agent should be sufficient to stabilize the metals other than alkali ions, taking into account their concentration and the pH of the solution in the solution.
  • the concentration can range between 0.1 and 30 g / l. It is preferably 0.5 to 1 g / l.
  • the aqueous alkaline solution for cleaning and degreasing the metal surface can be obtained by adding a solid concentrate which contains the alkaline-reacting cleaning agent or agents, the surfactant (s), the metal ions other than alkali ions and the complexing agent or agents.
  • the solution can also be obtained if solid or liquid concentrates are used, one of which contains the alkaline detergent (s), the total amount or only part of the necessary surfactant (s) and the total amount or only part of the necessary complexing agent contains and the other of which contains the metal cations other than alkali ions, the total amount or only part of the necessary surfactant (s) and the total amount or only part of the necessary complexing agent.
  • solid or liquid concentrates one of which contains the alkaline detergent (s), the total amount or only part of the necessary surfactant (s) and the total amount or only part of the necessary complexing agent contains and the other of which contains the metal cations other than alkali ions, the total amount or only part of the necessary surfactant (s) and the total amount or only part of the necessary complexing agent.
  • the cleaning and degreasing solutions described above can be sprayed or dipped at a temperature in the range from 20 to 90 ° C., preferably from 45 to 65 °, for a period of from about 3 to 180 seconds, preferably from 10 to 30 seconds. be applied.
  • the metal surface is then brought into contact with a solution which contains alkali, cations of at least one metal other than alkali ions and at least one complexing agent.
  • a solution which contains alkali, cations of at least one metal other than alkali ions and at least one complexing agent can be, for example, a solution as described in FR-PS-1 411 272.
  • the passivation solution can contain, for example, chromium-III and / or chromium-IV and have the properties described in FR-PS-1 487 183.
  • a conversion coating can be created by applying a dispersion of chromic acid and / or chromium compound with colloidal silicon dioxide.
  • the passivation solution applied for the passivation treatment is preferably dried.
  • the metal surface treated in this way is then provided with paint, lacquer and the like.
  • the inventive method is suitable for the surface treatment of objects which consist of zinc or zinc alloys or a coating of zinc or zinc alloys, such as. B. galvanized steel. It is particularly suitable for the treatment of sheet metal or strip.
  • Hot-dip galvanized steel sheets were used to carry out the tests.
  • the sheets were then rinsed with cold running water and containing a solution brought into contact. This was also done by spraying at a pressure of 1.5. 10 5 Pa for 10 sec, but at 65 ° C.
  • the sheets were coated with a coating of alkyd resin or acrylate resin with a thickness of approx. 30 1 1 m. After drying, the sheets rested for 48 hours.
  • Hot-dip galvanized steel sheets were treated according to the procedure in Example 1, but solutions of the following nature were used for cleaning and degreasing:
  • the varnishes applied by the roller application process were of the following type: polyvinyl chloride, polyester, silicone-modified polyester, polyvinylidene and polyacrylate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Claims (10)

1. Procédé de préparation de surfaces métalliques de zinc ou d'alliages de zinc pour l'application ultérieure de peinture, de laque, etc. par nettoyage alcalin et passivation par des revêtements de transformation chimique, caractérisé en ce que
a) on nettoie et on dégraisse la surface métallique avec une solution exempte de silicate, qui contient au moins un détergent à réaction alcaline, au moins un agent tensioactif, des cations d'au moins un métal différent des ions alcalins, et au moins un complexant dans une quantité suffisante pour stabiliser les cations métalliques en solution,
b) on la rince à l'eau,
c) on la met en contact avec une solution qui contient un alkali, des cations d'au moins un métal différent des ions alcalins, et au moins un complexant,
d) on la rince à l'eau,
e) puis on la traite ensuite par une solution de passivation acide.
2. Procédé suivant la revendication 1, caractérisé en ce qu'on nettoie et dégraisse la surface métallique avec une solution a) qui présente un pH de 11,5 à 12,5.
3. Procédé suivant les revendications 1 ou 2, caractérisé en ce qu'on nettoie et dégraisse la surface métallique avec une solution a) qui contient comme cations métalliques différents des ions alcalins des ions cobalt, fer et/ou nickel.
4. Procédé suivant les revendications 1, 2 ou 3, caractérisé en ce qu'on nettoie et dégraisse la surface métallique avec une solution a) qui contient des cations d'au moins un métal différent des ions alcalins dans des quantités de 50 à 5000 mg/1, de préférence de 100 à 1000 mg/1.
5. Procédé suivant une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'on nettoie et dégraisse la surface métallique avec une solution a) qui contient comme complexant du gluconate de sodium, du glucoheptonate de sodium, du sorbitol, et/ou de l'éthylènediaminetétraacétate.
6. Procédé suivant une ou plusieurs des revendications 1 à 5, caractérisé en ce qu'on nettoie et dégraisse la surface métallique avec une solution a) qui contient le complexant dans une quantité de 0,1 à 30 g/I, de préférence de 0,5 à 1 g/I.
7. Procédé suivant une ou plusieurs des revendications 1 à 6, caractérisé en ce qu'on nettoie et dégraisse la surface métallique avec une solution a) qui contient un agent tensioactif non-ionogéne.
8. Procédé suivant une ou plusieurs des revendications 1 à 7, caractérisé en ce qu'on nettoie et dégraisse la surface métallique avec une solution a) à une température de 20 à 90° C, de préférence de 45 à 65° C, pendant une durée de 3 à 180 sec., de préférence de 10 à 30 sec., par immersion et/ou pulvérisation.
9. Procédé suivant une ou plusieurs des revendications 1 à 8, caractérisé en ce qu'on traite la surface métallique dans le stade e) avec une solution, qui contient un composé du chrome, en particulier un chromate, et de l'acide silicique colloidal.
10. Procédé suivant une ou plusieurs des revendications 1 à 9, caractérisé en ce qu'on sèche la solution appliquée lors du traitement dans le stade e).
EP19850200318 1984-03-07 1985-03-05 Procédé de prétraitement de surfaces en zinc pour le laquage Expired EP0154384B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8403560 1984-03-07
FR8403560A FR2560894B1 (fr) 1984-03-07 1984-03-07 Procede de preparation de surfaces de zinc, d'alliages de zinc et d'acier recouvert de ces materiaux, destinees a recevoir des peintures ou des vernis

Publications (3)

Publication Number Publication Date
EP0154384A2 EP0154384A2 (fr) 1985-09-11
EP0154384A3 EP0154384A3 (en) 1987-02-04
EP0154384B1 true EP0154384B1 (fr) 1989-06-21

Family

ID=9301804

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19850200318 Expired EP0154384B1 (fr) 1984-03-07 1985-03-05 Procédé de prétraitement de surfaces en zinc pour le laquage

Country Status (3)

Country Link
EP (1) EP0154384B1 (fr)
DE (2) DE3507372A1 (fr)
FR (1) FR2560894B1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6220880A (ja) * 1985-07-19 1987-01-29 Nippon Parkerizing Co Ltd 亜鉛−アルミニウム合金めつき鋼板の表面処理方法
JPH0730458B2 (ja) * 1988-08-08 1995-04-05 日本パーカライジング株式会社 亜鉛又は亜鉛系めっき材料の黒色化処理方法
DE102010001686A1 (de) 2010-02-09 2011-08-11 Henkel AG & Co. KGaA, 40589 Zusammensetzung für die alkalische Passivierung von Zinkoberflächen
EP2503025B1 (fr) 2011-03-22 2013-07-03 Henkel AG & Co. KGaA Traitement en plusieurs étapes de protection contre la corrosion des pièces métalliques ayant au moins partiellement une surface en zinc ou en alliages de zinc

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2331196A (en) * 1941-08-22 1943-10-05 Westinghouse Electric & Mfg Co Protective phosphate coating
US3506499A (en) * 1964-03-16 1970-04-14 Yawata Seitetsu Kk Method of surface-treating zinc,aluminum and their alloys
FR1411272A (fr) * 1964-08-20 1965-09-17 Parker Ste Continentale Procédé pour le revêtement des surfaces de zinc et d'alliages de zinc
US3501352A (en) * 1965-08-02 1970-03-17 Hooker Chemical Corp Composition and method for treating zinc surfaces
FR1487183A (fr) * 1965-08-02 1967-06-30 Parker Ste Continentale Composition et procédé pour le traitement des surfaces métalliques
SE330305B (fr) * 1965-10-19 1970-11-09 Continentals Parker Sa Soc
FR1596007A (fr) * 1968-04-18 1970-06-15
US3620949A (en) * 1969-04-11 1971-11-16 Balm Paints Ltd Metal pretreatment and coating process
JPS51135840A (en) * 1975-05-21 1976-11-25 Nippon Packaging Kk Surface treatment process for zinc or zinc alloy

Also Published As

Publication number Publication date
EP0154384A3 (en) 1987-02-04
FR2560894A1 (fr) 1985-09-13
EP0154384A2 (fr) 1985-09-11
DE3571148D1 (en) 1989-07-27
FR2560894B1 (fr) 1988-11-18
DE3507372A1 (de) 1985-09-26

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