WO2003014417A1 - Traitement d'acier etame avant peinture - Google Patents

Traitement d'acier etame avant peinture Download PDF

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Publication number
WO2003014417A1
WO2003014417A1 PCT/EP2002/008228 EP0208228W WO03014417A1 WO 2003014417 A1 WO2003014417 A1 WO 2003014417A1 EP 0208228 W EP0208228 W EP 0208228W WO 03014417 A1 WO03014417 A1 WO 03014417A1
Authority
WO
WIPO (PCT)
Prior art keywords
treatment solution
range
treatment
aqueous treatment
silicate
Prior art date
Application number
PCT/EP2002/008228
Other languages
German (de)
English (en)
Inventor
Jörg Riesop
Reinhard Seidel
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP02767256A priority Critical patent/EP1412553A1/fr
Publication of WO2003014417A1 publication Critical patent/WO2003014417A1/fr

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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
    • C23C22/05—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

Definitions

  • the invention is in the field of treating tinned steel before painting.
  • Tinned steel also called tinplate
  • tinplate is mainly used for the production of cans, especially for the food sector.
  • the usual tin coatings for tinplate are about 1 to about 10 g / m 2 .
  • the amount of free tin can be 0.2 to 7 g / m 2 .
  • Tinplate objects are heated to temperatures in the range of 70 to 250 ° C for baking the lacquer and / or for sterilizing the contents of the container.
  • the tin oxidizes on the surface to tin oxide.
  • tin oxide has a lower reflectivity for light than elemental tin, the brightness of the surface decreases considerably due to the formation of tin oxide. This leads to an optically unsightly appearance and gives the impression that the surfaces are corroded.
  • the tin layer can oxidize almost completely to tin oxide, particularly in the case of tin layers thinned by drawing. This reveals the blue-gray color of the iron underneath the tin layer. This makes the surface even darker. Darkened surfaces, which may still be visible under a light layer of lacquer, can give the impression that the containers are corroded and the contents may be spoiled. Such containers are then heavier or no longer salable. Therefore, a pretreatment process for tinned surfaces is desirable, which reduces the tin oxide formation when heated, so that the surfaces largely retain their bright metallic appearance.
  • EP-B-533 823 describes a solution for treating the surface of tin-plated steel which contains 1 to 30 g / l phosphate ions, 0.1 to 5 g / l condensed phosphate ions and 0.1 to 20 g / l one contains water-soluble polyvinylphenol derivative.
  • the pH of the treatment solution must be in the range between 2.0 and 6.5, since the polyvinylphenol polymer fails at higher pH values.
  • the tinned surface is brought into contact with the treatment solution for a period of between 2 and 60 seconds. Then the surfaces are rinsed with tap water, then with deionized water and dried.
  • US 5 603 754 describes a treatment solution for tinned steel which has a pH in the range between 2.0 and 4.0. It contains at least 10 ppm of dissolved phosphate ions, but mainly at least one dissolved zirconium or titanium compound, an oxidizing agent and fluoride ions.
  • WO 93/18205 describes a cleaning solution for tinned steel, with which the surface is prepared for a subsequent corrosion-protective conversion treatment.
  • This cleaning solution has a pH in the range from 8 to 11 and contains 0.5 to 10 g / l of a builder component, for example phosphates or silicates, 0.05 to 1 g / l of a chelating complexing agent such as, for example, condensed phosphates, and 0.05 up to 2 g / l surfactant.
  • WO 94/13855 describes a treatment solution for tinned surfaces which has a pH in the range from 2.0 to 4.5 and which has 1 to 30 g / l phosphate ions, 0.1 to 5 g / l of a chelating complexing agent and 0 , 01 to 2.0 g / l of tin ions.
  • the chelating complexing agent can be, for example, condensed phosphate.
  • the invention relates to a method for treating the surface of tin-plated steel with an aqueous treatment solution containing phosphate or silicate, characterized in that a surface freshly produced or cleaned before the treatment is treated with an aqueous treatment solution with a pH value in the Range from 8 to 13.5, which contains 0.1 to 15 g / l phosphate, calculated as phosphorus, or 0.1 to 3 g / l silicate, calculated as silicon, for a period in the range from 1 to 30 seconds Brings contact and then dries the treatment solution without rinsing.
  • the treatment solution can be brought into contact with the metal surface by dipping, spraying or roller application.
  • the treatment solution preferably has a temperature in the range from 15 to 60 ° C.
  • the process can be used in a tinning plant immediately after the tinning. In this way, the treatment solution comes into contact with a freshly produced tinned surface. In this case, no cleaning is required between the tinning and the treatment method according to the invention. However, if the tinned surfaces are contaminated, for example with anti-corrosive oils or with drawing agents, it is necessary to clean and preferably rinse the surfaces with a conventional cleaner suitable for this purpose before the treatment according to the invention.
  • the process according to the invention can be used on the one hand for tinned strip, preferably directly after its production.
  • it is suitable for the treatment of objects made from tinned steel by forming processes such as deep drawing.
  • An example of such objects are cans, in particular those for holding food.
  • the surface is not rinsed with water after contact with the treatment solution. Rather, the treatment solution is dried on the surface. As a result, a layer of phosphate or silicate remains on the surface, which reduces the formation of tin oxide during a subsequent heat treatment.
  • the surfaces can be painted immediately. No further corrosion-protective conversion treatment is required.
  • phosphates are used in the process according to the invention, they are preferably selected from the group consisting of orthophosphate, diphosphate, triphosphate and / or higher condensed phosphates. Of course, one must choose those phosphates which are water-soluble in the concentration range given at the pH values mentioned. Alkali metal phosphates and in particular the sodium phosphates are preferred for this.
  • the aqueous treatment solution preferably has a pH in the range of at least 8 and in particular at least 8.5 to a maximum of 11, in particular a maximum of 10.5. Depending on the phosphate used, this pH value can be adjusted with NaOH or phosphoric acid.
  • a phosphate-containing solution is applied to the metal surface in the process according to the invention, after drying on the metal surface a layer coating in the range of 2 to 100 mg / m 2 , preferably 15 to 30 mg / m 2 phosphorus is obtained.
  • an aqueous solution of silicate is used.
  • silicates which are water-soluble in the concentration and pH range mentioned.
  • Alkali metal silicates with a molar ratio of SiO 2 : M 2 O, where M is an alkali metal, are preferably chosen in the range from 0.5 to 4, in particular in the range from 1 to 3.
  • Such alkali metal silicates are commercially available in solid form or in the form of aqueous solutions available.
  • a sodium water glass solution from Cognis can be used for this purpose, which is known commercially as type HK 37/40.
  • a treatment solution containing silicate preferably has a pH in the range from at least 9.5, in particular from at least 10 to a maximum of 13.5, in particular up to 13. If a pH in this range is not already available when the water glass solution is diluted or when the alkali metal silicate is dissolved, it can be adjusted upwards with sodium hydroxide solution, downwards with a less alkaline silicate solution or with sulfuric or nitric acid.
  • a layer coating in the range of 3 to 100 mg / m 2 , preferably 5 to 30 mg / m 2 of silicon is obtained after drying on the metal surface.
  • the layer of silicon or phosphor on the treated surface can be determined by conventional analytical techniques.
  • an X-ray fluorescence analysis is recommended after an appropriate calibration, since it works non-destructively and quickly delivers a result.
  • the treatment solution it is not necessary that the treatment solution contain other components, such as complexing agents other than Contains phosphates, organic polymers and / or complex fluorides.
  • complexing agents other than Contains phosphates, organic polymers and / or complex fluorides The additional use of organic polymers in particular could lead to stability problems in the alkaline treatment solutions.
  • organic polymers can have a negative impact on paint adhesion and corrosion behavior after the cans have been sterilized. Accordingly, it is preferred in the process according to the invention that the aqueous treatment solution does not contain more than 1 mg / l of complexing agents other than phosphates, organic polymers and / or complex fluorides.
  • drainage aids are agents for reducing the surface tension of H 2 O, for example surfactants.
  • Such drainage aids reduce the formation of water stains after the treatment solution has dried out.
  • the treatment solution can contain agents to facilitate sliding. These reduce the friction between the tinplate objects, for example the cans, during transport processes.
  • the treatment method according to the invention replaces a conventional conversion treatment such as phosphating or chromating. Accordingly, a particular aspect of the method is that the metal surface is painted after the aqueous treatment solution has dried without further corrosion protection treatment, such as conversion treatment, being carried out between the treatment according to the invention and the painting.
  • the present invention relates to an article made of tinned steel which has a coating on the tin layer with phosphate or silicate with a layer coating of 2 to 100 mg / m 2 phosphorus or 3 to 100 mg / m 2 silicon.
  • the object can consist of a tinned steel strip or a section thereof.
  • the article can be a shaped part such as a can, especially a can for holding food.
  • the object can carry a lacquer layer above the phosphate or silicate layer. If the object coated according to the invention is a steel strip or a section thereof, an additional advantage of the coating according to the invention is that forming oils spread better on the coated surface than without such a coating.
  • the most important advantage of the treatment according to the invention is that it reduces the formation of tin oxide when the tinplate objects are heated. As a result, the surface retains a more metallic appearance than without the treatment according to the invention.
  • food cans have a "fresher" effect on a buyer than cans that have not been treated according to the invention.
  • solution A a solution containing 3 g / l silicon was used as solution A. This was prepared by diluting a commercial sodium water glass solution (type HK 37/40, company Cognis). It had a pH of 10.8. A sodium pyrophosphate solution with 3 g / l phosphorus was used as solution B. It had a pH of 8.5.
  • the treatment solutions were applied to flat tinplate with rollers with a wet film thickness of 6 ⁇ m and dried at a temperature of 75 ° C. after an exposure time of 1 second.
  • the sheets were then annealed at a temperature of 220 ° C. for a period of 15 minutes. The results are shown in the list below.
  • Cleaned tin cans were immersed in treatment solutions at a temperature of 40 ° C for 6 seconds and then dried at 50 ° C.
  • the treatment solutions with different concentrations of silicon or phosphorus were prepared analogously to embodiment 1.
  • the tempering conditions also corresponded to Example 1.
  • the table below contains the results. Tin cans, applied for 6 seconds at 40 ° C

Abstract

L'invention concerne un traitement de la surface d'acier étamé comprenant une solution de traitement aqueuse contenant du phosphate ou silicate. Ce procédé est caractérisé en ce qu'avant le traitement, on met en contact pendant une période de 1 à 30 secondes une surface fraîchement produite ou nettoyée avec une solution de traitement aqueuse d'un pH compris entre 8 et 13,5. Cette solution contient 0 ;1 à 15 g/l de phosphate, calculé comme phosphore, ou 0,1 à 3 g/l de silicate, calculé comme silicium. Ensuite, on sèche la solution de traitement sans rinçage.
PCT/EP2002/008228 2001-08-03 2002-07-24 Traitement d'acier etame avant peinture WO2003014417A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02767256A EP1412553A1 (fr) 2001-08-03 2002-07-24 Traitement d'acier etame avant peinture

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2001138096 DE10138096A1 (de) 2001-08-03 2001-08-03 Behandlung von verzinntem Stahl vor einer Lackierung
DE10138096.8 2001-08-03

Publications (1)

Publication Number Publication Date
WO2003014417A1 true WO2003014417A1 (fr) 2003-02-20

Family

ID=7694248

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/008228 WO2003014417A1 (fr) 2001-08-03 2002-07-24 Traitement d'acier etame avant peinture

Country Status (3)

Country Link
EP (1) EP1412553A1 (fr)
DE (1) DE10138096A1 (fr)
WO (1) WO2003014417A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB535670A (en) * 1939-10-18 1941-04-17 Victor Alexander Lowinger Improved process for the treatment of tinplate and tinplate articles
US2306143A (en) * 1939-05-09 1942-12-22 Continental Can Co Preparing metal surfaces to resist staining or corrosion
JPS54158341A (en) * 1978-06-05 1979-12-14 Nippon Packaging Kk Surface treatment of tin plated steel plate and can
WO1993018205A1 (fr) * 1992-03-13 1993-09-16 Henkel Corporation Composition et procede destines a nettoyer du materiau en tole

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2306143A (en) * 1939-05-09 1942-12-22 Continental Can Co Preparing metal surfaces to resist staining or corrosion
GB535670A (en) * 1939-10-18 1941-04-17 Victor Alexander Lowinger Improved process for the treatment of tinplate and tinplate articles
JPS54158341A (en) * 1978-06-05 1979-12-14 Nippon Packaging Kk Surface treatment of tin plated steel plate and can
WO1993018205A1 (fr) * 1992-03-13 1993-09-16 Henkel Corporation Composition et procede destines a nettoyer du materiau en tole

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 198019, Derwent World Patents Index; Class E13, AN 1980-33303C, XP002218747 *
NUTTER A.: "AMERICAN CHEMICAL SOCIETY.", CHEMICAL ABSTRACTS + INDEXES, AMERICAN CHEMICAL SOCIETY. COLUMBUS, US, vol. 14, no. 2, 14 January 1991 (1991-01-14), COLUMBUS, US, pages 226, XP000213066, ISSN: 0009-2258 *

Also Published As

Publication number Publication date
DE10138096A1 (de) 2003-02-13
EP1412553A1 (fr) 2004-04-28

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