EP2208809A1 - Coating composition for a metallic substrate - Google Patents

Coating composition for a metallic substrate Download PDF

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Publication number
EP2208809A1
EP2208809A1 EP20100159057 EP10159057A EP2208809A1 EP 2208809 A1 EP2208809 A1 EP 2208809A1 EP 20100159057 EP20100159057 EP 20100159057 EP 10159057 A EP10159057 A EP 10159057A EP 2208809 A1 EP2208809 A1 EP 2208809A1
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EP
European Patent Office
Prior art keywords
coating
weight
film
coating composition
dry
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EP20100159057
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German (de)
French (fr)
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EP2208809B1 (en
EP2208809B9 (en
Inventor
Jean-Marie Poulet
Alain Chesneau
Georges Leger
Denis Begue
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NOF Metal Coatings Europe
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NOF Metal Coatings Europe
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    • 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
    • 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
    • C23C22/66—Treatment of aluminium or alloys based thereon
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the present invention relates to a metal substrate coating composition based on an aqueous solution of sodium silicate and / or potassium and / or lithium.
  • the present invention also relates to methods of applying this composition to said metal substrate and to the various uses of this coating composition.
  • the coating composition is intended to be applied to a steel substrate having a free outer surface consisting of a metal layer of zinc or zinc-based alloy.
  • said metal layer may have been deposited on said steel substrate electrolytically or by hot dipping.
  • the metal surface treatment is subject to multiple constraints of a technical, economic and environmental nature.
  • Sheet metal coils are produced by steelmakers using very fast processes, with line speeds ranging from a few m / min up to 250 m / min.
  • the surface treatment technologies must accommodate these line speed constraints.
  • Technical difficulties can then appear if it is desired to maintain a good chemical reactivity between the substrate and the treatment products, but also in terms of film formation, if one wishes to obtain a good tension and a good homogeneity of the film deposits.
  • Anti-corrosion treatment technologies usually use chromium-based products (hexavalent or trivalent) that are applied in one or more layers. However, these products are harmful to the environment and need to be replaced by non-environmental treatment products.
  • on-line operating constraints also require products that are on the one hand mono-component (that is to say that do not require the preparation of a mixture of several products prior to industrial implementation) and which are, on the other hand, stable over time (that is to say, with a lifespan of more than 3 weeks to accommodate the productions made by campaign).
  • the present invention relates to a composition that meets the requirements and constraints mentioned above.
  • the coating composition is intended to be applied to a metal substrate.
  • the wet film thus obtained is then dried and gives rise to a dry coating film.
  • the coating composition preferably contains 5 to 30% by weight of sodium and / or potassium and / or lithium silicate (s), more preferably 5 to 20% by weight of sodium silicate (s) and / or potassium and / or lithium, more preferably 8 to 15% by weight of sodium silicate (s) and / or potassium and / or lithium.
  • this coating composition can be prepared in the form of a concentrate in which the percentage of sodium silicate (s) and / or potassium and / or lithium can reach up to about 40% by weight, or in the form of a powder in which the percentage of silicate (s) of sodium and / or potassium and / or lithium can reach up to about 80% by weight.
  • This sodium silicate solution may also contain a small proportion of Na 2 CO 3 of the order of 0.1% by weight relative to the weight of the silicate solution.
  • the present invention also relates to the dry coating film obtainable from the application method (described below) of the coating composition on a metal substrate.
  • This dry coating film is characterized in that it comprises at least 40% by weight of sodium silicate (s) and / or potassium and / or lithium silicate solids, preferably between 60% and 99.9% by weight relative to the total weight of dry film coating.
  • tensioning agent means an additive whose function is to lower and control the liquid surface energy of the composition (or surface tension).
  • Surface energy is the energy required to bring the molecules of the liquid interior of the composition to its surface. The lower the surface energy of the composition, the greater the wettability of the surface of the metal substrate. Wettability is the ability for said substrate to receive a liquid allowing it to spread over the largest possible area.
  • the surface energy of the composition is preferably adjusted to obtain good wettability of the surface to be coated under high line speed conditions before the product is frozen upon entering the drying zone.
  • the coating composition contains between 0.01 and 1% by weight of a tensioning agent, preferably about 0.1% by weight of a tensioning agent.
  • the tensioning agent may be added separately or on the occasion of the incorporation of another component containing such an agent, for example a dispersion or an emulsion of a polymer.
  • voltage agent may be mentioned polypropylene glycol and polyethylene glycol copolymers (such as Pluronic ® PE 3100 manufactured by BASF), silicone resins (such as ® BYK348, manufactured by BYK ), acetylenic glycols (such as Dyno1604 ® , manufactured by Air Products), anionic and nonionic mixtures (such as Dapro W95 HS ® , marketed by Elementis), quaternary ammoniums (such as Cycloquart ® , manufactured by Clariant), polyethoxylated alcohols modified (such as Triton ® DF16, manufactured by Union Carbide), and compatible mixtures thereof.
  • polypropylene glycol and polyethylene glycol copolymers such as Pluronic ® PE 3100 manufactured by BASF
  • silicone resins such as ® BYK348, manufactured by BYK
  • acetylenic glycols such as Dyno1604 ® , manufactured by Air Products
  • anionic and nonionic mixtures
  • the tensioning agent can be added to the composition according to the present invention in the form of an aqueous solution, a dispersion or an emulsion in water, with or without a co-solvent.
  • the water used in the coating composition according to the present invention is first subjected to a deionization process such that the conductivity of this water is approximately less than 20 ⁇ S / cm.
  • the pH of the coating composition may be an alkaline pH, preferably between 11 and 13, more preferably between 11 and 12.
  • the coating composition may further contain a polymer whose function is to lower the glass transition temperature of the dry coating film.
  • the presence of said polymer imparts elasticity and flexibility properties to the dry film of coating thus obtained. Said polymer then makes it possible to reduce or eliminate the appearance of cracks in the dry coating film, during a subsequent mechanical deformation of the metal substrate.
  • acrylic polymers or copolymers such as Polysol M-19 ® (manufactured by SHOWA Highpolymer Co. Ltd.) or Rhodopas D-20 40 ® (manufactured by Rhodia), polyurethanes, alkyds, epoxy esters, as well as their compatible mixtures.
  • said polymer can be added to the composition according to the present invention in the form of a dispersion or an emulsion in water or of an aqueous solution, in a proportion which advantageously allows to reach up to 60 % by weight of the dry coating film.
  • said polymer can at the same time provide the composition with the previously mentioned tensioning agent.
  • the coating composition may furthermore contain an additive making it possible to increase the hydrophobicity of the dry coating film, in a proportion which advantageously makes it possible to attain up to 50% by weight of the film dry coating, preferably up to 25% by weight of the dry film coating.
  • This additive is advantageously a silane, preferably chosen from di- or trimethoxysilanes, or functionalized di- or triethoxysilanes, as well as their mixtures.
  • the organic functionality can be vinyl, amine or oxyrane (epoxy) type.
  • the silane is chosen from epoxy functional silanes such as beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 4- (trimethoxysilyl) 1,2-butane-epoxide or gamma-glycidoxypropyltrimethoxysilane.
  • the silane may also act as a binder, a stabilizer for the coating composition, and may increase the corrosion resistance of the dry coating film.
  • silanes can be used independently or in combination in prehydrolysed form or not.
  • silane may also be associated with the addition of Titanate or Zirconate to enhance the crosslinking of the binder system depending on the characteristics required of the coating.
  • the increase in the hydrophobicity of the dry film coating can be observed visually, especially during cyclic corrosion tests (DIN 50017KTW), by the formation of condensed water vapor droplets (from the electrolyte) less spread than in the case of a coating whose binder is only composed of silicate.
  • the introduction of the silane into the coating composition leads to the decrease of the permeability and / or porosity of the dry film coating to the electrolyte, thereby conferring its hydrophobicity.
  • the hydrophobicity of the dry coating film obtained by introducing the silane into the coating composition allows a lower dry film thickness to be applied for the same corrosion resistance result.
  • the coating composition may furthermore contain an additive making it possible to reduce the free surface alkalinity of the dry coating film, in a proportion which advantageously makes it possible to attain up to 25% by weight. dry film coating.
  • This additive is preferably a cerium (Ce) salt, a Lanthanum salt (La), a molybdenum salt (Mo), molybdic acid, para-toluenesulphonic acid and their salts, or a polyol such as as glycerol, as well as their mixtures.
  • the coating composition may furthermore contain an additive making it possible to increase the anticorrosion properties of the dry coating film, in a proportion which advantageously makes it possible to attain up to 25% by weight of the film dry coating.
  • This additive is preferably a mineral binder such as a titanate or a zirconate, and mixtures thereof.
  • the coating composition may further contain a lubricating agent.
  • a lubricating agent such as synthetic organic polymers such as polytetrafluoroethylene, polyethylene, polyethylene glycol or natural organic polymers such as carnauba wax or paraffins, as well as mixtures thereof.
  • the lubricant is added to the coating composition in a proportion which advantageously makes it possible to attain up to 15% by weight of the dry coating film, preferably between 1.5 and 15% by weight of the dry coating film, more preferably between 3 and 15% by weight of the dry coating film, more preferably between 5 and 15% by weight of the dry coating film.
  • the lubricant may require a stabilizer to avoid phase separation in the coating composition.
  • organophilic clays natural or synthetic
  • silica derivatives cellulose derivatives
  • xanthan gum or associative thickeners of polyurethane or acrylic type, and mixtures thereof.
  • the stabilizer is added to the coating composition according to the present invention in a proportion which achieves between about 0.1 and 5% by weight of the dry coating film.
  • the coating composition may additionally be added with an antifoam agent chosen in a manner compatible with the other constituents of the coating composition and the optimal amount of which is determined according to the conventional experiments of routines known to those skilled in the art.
  • said composition may be substantially free of organic solvent.
  • organic solvents have been found, in practice, to be incompatible with sodium and / or potassium and / or lithium silicates, the main constituents of the coating composition.
  • the present invention also relates to a method of coating a metal substrate which comprises applying the previously described coating composition to the surface of said substrate.
  • the application of the coating composition described above is carried out during an operation which consists in depositing a wet film of said composition, of suitable low thickness, followed by a drying operation of said composition.
  • metal substrate thus coated, giving rise to a dry coating film of said substrate.
  • the wet film thickness of the coating composition deposited on the metal substrate is between 0.3 and 39 ⁇ m, preferably between 0.3 and 30 ⁇ m and the wet film is applied at a rate of 0.6 at 40 g / m 2 , preferably from 0.6 to 24 g / m 2 .
  • the method which is the subject of the present invention can be carried out online, after the metal coating step of zinc or zinc-based alloy of the steel substrate, or on a recovery line such as on a pre-lacquering line (" coil-coating ").
  • the operation of depositing the wet film of the coating composition on the metal substrate can advantageously be carried out by spraying, spraying followed by a spinning operation, by soaking followed by spinning operation or by means of a coating system composed of at least one roller.
  • the spinning operation makes it possible to control the thickness of the wet film deposited on the metal substrate.
  • This spinning operation can be advantageously carried out using a set of spinning rolls.
  • the drying operation of the metal substrate coated with the wet film is carried out by heating the metal substrate or the wet film so as to bring the latter to a temperature of between room temperature and room temperature. ° C.
  • the heating operation can be performed directly by induction, or indirectly by convection or infrared. Convection heating generally requires a longer drying time than induction heating or infrared heating.
  • This drying operation is advantageously carried out by heating the metal substrate or the wet film so as to bring the latter preferably to a temperature of at least about 35 ° C for a period of at least 2 seconds if heating is used. convection and for a maximum of 10 seconds, preferably 5 seconds, more preferably 1 to 2 seconds, if using induction heating or infrared heating.
  • the drying operation is carried out in order to obtain a dry film thickness of coating of between 0.05 and 0.80 ⁇ m, preferably between 0.05 and 0.60 ⁇ m and so as to obtain a weight of layer of dry film coating between 0.1 g / m 2 and 1.3 g / m 2 , preferably between 0.2 g / m 2 and 1.2 g / m 2 , more preferably between 0.2 and 0.5 g / m 2 .
  • the operations of deposition of the wet film and of drying are carried out between the operations of metal coating based on zinc or zinc alloy of the steel substrate and final winding.
  • the present invention also relates to the various uses of the coating composition object of the present invention.
  • the coating composition can be used as a corrosion protection layer of metal sheets when it is applied to said sheets.
  • said composition may be used as an anti-corrosion protection layer for metal sheets intended to be temporarily stored.
  • a layer of dry coating film according to the present invention when it has been applied to a metal substrate and then dried at 240 ° C., completely resists said soak baths. degreasing.
  • said layer of dry coating film is partially solubilized by the degreasing baths and when it has been dried at 50 ° C., it is completely solubilized by the degreasing baths. .
  • the coating composition can be used as a lubricating layer when it further contains a lubricant and is applied to metal sheets for shaping, particularly for folding, bending and stamping said metal sheets.
  • the coating composition may be used as an anti-fingerprint agent.
  • metal sheets coated with the coating composition which is the subject of the present invention can be handled. as such, without fingerprints remaining subsequently printed on said metal sheets.
  • the coating composition may be applied to metal substrate parts to be welded.
  • said substrates thus coated retain their weldability property and the welding operations can be done directly.
  • the coating composition may require the addition of conductive pigments such as iron phosphide, ammonium silicate, nickel, tungsten, zinc (pure or alloyed) and carbon, as well as their mixtures.
  • conductive pigments such as iron phosphide, ammonium silicate, nickel, tungsten, zinc (pure or alloyed) and carbon, as well as their mixtures.
  • Example 1 Sodium silicate coating composition (A)
  • Lubricated coating composition (B) % mass Sodium silicate 10.8 Polytetrafluoroethylene (PTFE) 0.7 Polyethylene (PE) 1.3 Acrylic polymer 1.1 Water 86.1 Composition of lubricated dry coating film (B) % mass Sodium silicate 78 Acrylic polymer 8 PTFE and PE 14
  • Example 5 Surface energy of the coating composition as a function of the tensioning agent
  • the test consists of subjecting the metal substrate sample to a friction over a length of about 50 mm (see FIG. figure 1 ).
  • the samples have a size of 50 mm x 200 mm and are processed on both sides.
  • a lateral force (F L ) is imposed on the sample and it is subjected to a constant speed pull of 20 mm / min.
  • the tensile force F T is measured after a friction distance of 50 mm.
  • the measurement temperature is 21 ⁇ 2 ° C.
  • the coating dry film layer weights deposited on the metal substrate samples are between 1 and 1.2 g / m 2 .
  • the reference sample is an electrogalvanised sheet (7.5 ⁇ m on each side) on which a layer of ANTICORRIT 4107 S ® oil (manufacturer FUCHS) has been applied at a height of 2.5 g / m 2 on each face .
  • This oil is widely used in the automotive industry as a lubricant for sheet metal for stamping.
  • composition of dry coating film Composition of the lubricating agent contained in the composition of the dry coating film (percentages expressed by weight of dry matter) ⁇ (B1) 75% PTFE 0.18 25% PEG (B2) 50% PTFE 0.176 50% PEG (B3) 25% PTFE 0.177 25% PEG 50% PE (B4) 17% PTFE 0.169 50% PEG 33% PE (B5) 34% PTFE 0.178 66% PE (B6) 100% PEG 0.203
  • the coefficients of friction of the samples coated with a dry film of composition according to the present invention (B1) to (B6) are lower than the coefficient of friction of the reference sample. This indicates that lubrication of the dry film-coated samples of the present invention (B1) to (B6) is better than that of the reference sample.
  • Sample hot-dip galvanized steel (10 ⁇ m) Sample of hot-dip galvanized steel (10 ⁇ m) coated with a dry film of coating according to composition (A) with a weight of layer equal to: 0.3 g / m 2 0.6 g / m 2 0.9 g / m 2 1.2 g / m 2 Humidotherm test (duration 15 cycles) performed according to DIN 50017 White rust on 100% of the surface (after 5 cycles only) Change in appearance: White rust on 70% of the surface No appearance changes No appearance changes No appearance changes No appearance changes Salt spray test (48 hours duration) according to ISO 9227 White rust on 100% of the surface (after 24 hours only) White rust on 60% of the surface White rust on 20% of the surface White rust on less than 5% of the surface No appearance changes
  • Test DIN 50017KTW (20 cycles) Hot-dip galvanized steel substrate (10 ⁇ m) coated with a dry coating film according to composition (A) or (E) with a coating weight of: 0.2 g / m 2 0, 5 g / m 2 0.65 g / m 2 Formulation (A) Change in appearance: white rust on 90% of the surface Change in appearance: white rust on 50% of the surface Very slight change in appearance: white rust on 15% of the surface Formulation (E) Very slight change in appearance: white rust on 20% of the surface No change in appearance No change in appearance No change in appearance No change in appearance No change in appearance
  • composition comprising the silane is more effective against corrosion than the silane-free composition.
  • introduction of silane thus makes it possible to reduce the weight of the layer while maintaining the same anticorrosion properties.

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Abstract

A coating composition (I) for metal substrates with an outer surface consisting of a layer of zinc or aluminum or their alloys contains: (A) 5-30 wt% sodium, potassium or lithium silicate; (B) 0-1 wt% surfactant; and (C) water (to 100%). Independent claims are also included for (1) metallic substrates coated with (I) (2) a method for the application of (I) to metal substrates as above by depositing a suitably thin, wet film of (I) and then drying the film.

Description

La présente invention a pour objet une composition de revêtement de substrat métallique à base d'une solution aqueuse de silicate de sodium et/ou de potassium et/ou de lithium.The present invention relates to a metal substrate coating composition based on an aqueous solution of sodium silicate and / or potassium and / or lithium.

La présente invention se rapporte également aux procédés d'application de cette composition sur ledit substrat métallique et aux diverses utilisations de cette composition de revêtement.The present invention also relates to methods of applying this composition to said metal substrate and to the various uses of this coating composition.

Selon la présente invention, la composition de revêtement est destinée à être appliquée sur un substrat en acier présentant une surface extérieure libre constituée par une couche métallique de zinc ou d'alliage à base de zinc.According to the present invention, the coating composition is intended to be applied to a steel substrate having a free outer surface consisting of a metal layer of zinc or zinc-based alloy.

Dans un mode de réalisation avantageux, ladite couche métallique peut avoir été déposée sur ledit substrat en acier par voie électrolytique ou par immersion à chaud.In an advantageous embodiment, said metal layer may have been deposited on said steel substrate electrolytically or by hot dipping.

A titre d'exemple de substrats métalliques, on mentionnera :

  • les tôles électrozinguées : substrat en acier revêtu d'une couche de zinc appliquée par voie électrolytique,
  • les tôles galvanisées à chaud : substrat en acier revêtu d'une couche de zinc appliquée par immersion de la dite tôle dans un bain de zinc en fusion,
  • GALFAN : substrat en acier revêtu d'une couche d'alliage de zinc (95% en poids) et d'aluminium (5% en poids) appliquée par immersion dans un bain d'alliage de zinc et d'aluminium dans les mêmes proportions en fusion,
  • GALVALUME® : substrat en acier revêtu d'une couche d'alliage d'aluminium (55% en poids) et de zinc (45% en poids) appliquée par immersion dans un bain d'alliage d'aluminium et de zinc dans les mêmes proportions en fusion.
As an example of metal substrates, mention will be made of:
  • electrogalvanized sheets: steel substrate coated with an electrolytically applied zinc layer,
  • hot-dip galvanized sheets: zinc coated steel substrate applied by immersing said sheet in a bath of molten zinc,
  • GALFAN: steel substrate coated with a layer of zinc alloy (95% by weight) and aluminum (5% by weight) applied by immersion in a bath of zinc and aluminum alloy in the same proportions in fusion,
  • GALVALUME ® : steel substrate coated with a layer of aluminum alloy (55% by weight) and zinc (45% by weight) applied by immersion in a bath of aluminum alloy and zinc in the same molten proportions.

Le traitement de surface métallique est soumis à de multiples contraintes à la fois d'ordre technique, économique et environnemental.The metal surface treatment is subject to multiple constraints of a technical, economic and environmental nature.

La production des bobines de tôle chez les sidérurgistes s'effectue par des procédés très rapides dont la vitesse de ligne peut aller de quelques m/min jusqu'à 250 m/min. Lorsque l'on souhaite coupler au procédé de production une étape de traitement de surface, les technologies de traitement de surface doivent s'accommoder de ces contraintes de vitesse de ligne. Des difficultés techniques peuvent alors apparaître si l'on souhaite conserver une bonne réactivité chimique entre le substrat et les produits de traitement, mais aussi au niveau de la formation de film, si l'on souhaite obtenir un bon tendu et une bonne homogénéité des dépôts de film.Sheet metal coils are produced by steelmakers using very fast processes, with line speeds ranging from a few m / min up to 250 m / min. When it is desired to couple the production process with a surface treatment step, the surface treatment technologies must accommodate these line speed constraints. Technical difficulties can then appear if it is desired to maintain a good chemical reactivity between the substrate and the treatment products, but also in terms of film formation, if one wishes to obtain a good tension and a good homogeneity of the film deposits.

Les technologies de traitement anticorrosion font habituellement appel à des produits à base de chrome (hexavalent ou trivalent) qui sont appliqués en une ou plusieurs couches. Ces produits sont toutefois néfastes pour l'environnement et nécessitent d'être remplacés par des produits de traitement sans impact sur l'environnement.Anti-corrosion treatment technologies usually use chromium-based products (hexavalent or trivalent) that are applied in one or more layers. However, these products are harmful to the environment and need to be replaced by non-environmental treatment products.

De plus, les industriels cherchent aujourd'hui à mettre en oeuvre une technologie satisfaisant un cahier des charges minimal et capable d'être fonctionnalisée afin de satisfaire des niveaux d'exigence plus élevés et d'accroître la valeur ajoutée du traitement de surface.In addition, industrialists are now seeking to implement a technology that meets minimum specifications and is capable of being functionalized in order to meet higher requirements and to increase the added value of surface treatment.

En complément à la résistance à la corrosion, la fonctionnalisation des traitements concerne notamment les domaines suivants:

  • les propriétés de surface telles que le caractère hydrophobe ou hydrophile de la surface, le caractère anti-empreinte digitale de la surface ou bien encore la modification de l'alcalinité libre de la surface,
  • les propriétés de mise en oeuvre telles que la flexibilité et la lubrification du revêtement pour les opérations de pliage ou emboutissage, mais aussi la conductivité électrique pour l'assemblage par soudage.
In addition to the resistance to corrosion, the functionalization of the treatments concerns in particular the following areas:
  • the surface properties such as the hydrophobic or hydrophilic nature of the surface, the anti-fingerprint nature of the surface or even the modification of the free alkalinity of the surface,
  • the processing properties such as the flexibility and the lubrication of the coating for the bending or stamping operations, but also the electrical conductivity for the welding assembly.

Les industriels sont en outre soumis à des contraintes économiques et recherchent ainsi des traitements compacts à partir de formulations qui sont d'une part préparées en milieu aqueux (et qui ne nécessitent donc pas d'investissement complémentaire pour le retraitement d'éventuels solvants organiques) et qui permettent d'autre part l'application d'une seule couche avec un seul séchage.Manufacturers are also subject to economic constraints and are looking for compact treatments from formulations that are firstly prepared in aqueous medium (and therefore do not require additional investment for the reprocessing of possible organic solvents) and which allow the other hand the application of a single layer with a single drying.

Enfin les contraintes d'exploitation sur ligne exigent également des produits qui sont d'une part mono-composant (c'est-à-dire qui ne nécessitent pas la préparation d'un mélange de plusieurs produits préalablement à la mise en oeuvre industrielle) et qui sont d'autre part stables dans le temps (c'est-à-dire d'une durée de vie supérieure à 3 semaines pour s'accommoder des productions faites par campagne).Finally, on-line operating constraints also require products that are on the one hand mono-component (that is to say that do not require the preparation of a mixture of several products prior to industrial implementation) and which are, on the other hand, stable over time (that is to say, with a lifespan of more than 3 weeks to accommodate the productions made by campaign).

La présente invention a pour objet une composition qui satisfait aux exigences et contraintes précédemment mentionnées.The present invention relates to a composition that meets the requirements and constraints mentioned above.

La composition de revêtement selon la présente invention est caractérisée en ce qu'elle comprend (% en poids):

  • silicate(s) de sodium et/ou de potassium et/ou de lithium    3 à 35 %
  • agent de tension    0,01 % à 1 %
  • eau    qsp 100 %
The coating composition according to the present invention is characterized in that it comprises (% by weight):
  • silicate (s) of sodium and / or potassium and / or lithium 3 to 35%
  • tension agent 0.01% to 1%
  • water qs 100%

Ledit silicate de sodium et/ou de potassium et/ou de lithium et ledit agent de tension sont explicités plus loin dans la présente description.Said sodium and / or potassium and / or lithium silicate and said tensioning agent are explained later in the present description.

Comme précédemment indiqué, la composition de revêtement est destinée à être appliquée sur un substrat métallique. Le film humide ainsi obtenu est ensuite séché et donne naissance à un film de revêtement sec.As previously indicated, the coating composition is intended to be applied to a metal substrate. The wet film thus obtained is then dried and gives rise to a dry coating film.

Sauf indication contraire, tous les pourcentages indiqués dans le cadre de la présente description sont des pourcentages exprimés en poids par rapport au poids total de ladite composition de revêtement sous forme liquide. Dans le cas contraire, les proportions des constituants sont exprimées par rapport au film sec de revêtement, c'est-à-dire en poids de matière sèche par rapport au poids total du film sec de revêtement obtenu.Unless otherwise indicated, all the percentages indicated in the context of the present description are percentages expressed by weight relative to the total weight of said coating composition in liquid form. In the opposite case, the proportions of the constituents are expressed with respect to the dry film of coating, that is to say, by weight of dry matter relative to the total weight of the dry film of coating obtained.

La composition de revêtement contient de préférence 5 à 30 % en poids de silicate(s) de sodium et/ou de potassium et/ou de lithium, plus préférentiellement 5 à 20 % en poids de silicate(s) de sodium et/ou de potassium et/ou de lithium, encore plus préférentiellement 8 à 15% en poids de silicate(s) de sodium et/ou de potassium et/ou de lithium.The coating composition preferably contains 5 to 30% by weight of sodium and / or potassium and / or lithium silicate (s), more preferably 5 to 20% by weight of sodium silicate (s) and / or potassium and / or lithium, more preferably 8 to 15% by weight of sodium silicate (s) and / or potassium and / or lithium.

Avantageusement, cette composition de revêtement peut être préparée sous forme de concentrat dans lequel le pourcentage en silicate(s) de sodium et/ou de potassium et/ou de lithium peut atteindre jusqu'à environ 40 % en poids, ou bien sous forme de poudre dans laquelle le pourcentage en silicate(s) de sodium et/ou de potassium et/ou de lithium peut atteindre jusqu'à environ 80 % en poids.Advantageously, this coating composition can be prepared in the form of a concentrate in which the percentage of sodium silicate (s) and / or potassium and / or lithium can reach up to about 40% by weight, or in the form of a powder in which the percentage of silicate (s) of sodium and / or potassium and / or lithium can reach up to about 80% by weight.

Dans le cadre de la présente invention, le silicate de sodium peut être utilisé dans ladite composition sous la forme d'une solution aqueuse de silicate de sodium de composition pondérale suivante:

  • SiO2    20 à 40% en poids
  • Na2O    5 à 20 % en poids
  • eau    qsp 100 % en poids
In the context of the present invention, the sodium silicate can be used in said composition in the form of an aqueous solution of sodium silicate of the following weight composition:
  • SiO 2 20 to 40% by weight
  • Na 2 O 5 to 20% by weight
  • water qs 100% by weight

Cette solution de silicate de sodium peut également contenir une faible proportion de Na2CO3 de l'ordre de 0,1 % en poids par rapport au poids de la solution de silicate.This sodium silicate solution may also contain a small proportion of Na 2 CO 3 of the order of 0.1% by weight relative to the weight of the silicate solution.

Le silicate de potassium peut être utilisé dans ladite composition sous la forme d'une solution aqueuse de silicate de potassium de composition pondérale suivante:

  • SiO2    15 à 35% en poids
  • K2O    5 à 35% en poids
  • eau    qsp 100 % en poids
The potassium silicate may be used in said composition in the form of an aqueous solution of potassium silicate of the following weight composition:
  • SiO 2 15 to 35% by weight
  • K 2 O 5 to 35% by weight
  • water qs 100% by weight

Le silicate de lithium peut être utilisé dans ladite composition sous la forme d'une solution aqueuse de silicate de lithium de composition pondérale suivante:

  • SiO2    15 à 40% en poids
  • Li2O    1 à 10 % en poids
  • eau    qsp 100 % en poids
The lithium silicate may be used in said composition in the form of an aqueous solution of lithium silicate of the following weight composition:
  • SiO 2 15 to 40% by weight
  • Li 2 O 1 at 10% by weight
  • water qs 100% by weight

La présente invention a également pour objet le film sec de revêtement susceptible d'être obtenu à partir du procédé d'application (décrit ci-après) de la composition de revêtement sur un substrat métallique. Ce film sec de revêtement est caractérisé en ce qu'il comprend au moins 40 % en poids de matière sèche de silicate(s) de sodium et/ou de potassium et/ou de lithium, de préférence entre 60% et 99,9% en poids par rapport au poids total de film sec de revêtement.The present invention also relates to the dry coating film obtainable from the application method (described below) of the coating composition on a metal substrate. This dry coating film is characterized in that it comprises at least 40% by weight of sodium silicate (s) and / or potassium and / or lithium silicate solids, preferably between 60% and 99.9% by weight relative to the total weight of dry film coating.

Au sens de la présente invention, on entend par « agent de tension » un additif dont la fonction est d'abaisser et de contrôler l'énergie de surface liquide de la composition (ou tension superficielle). L'énergie de surface est l'énergie nécessaire pour amener les molécules de l'intérieur du liquide de la composition à sa surface. Plus l'énergie de surface de la composition est faible, plus la mouillabilité de la surface du substrat métallique est importante. La mouillabilité est la faculté pour ledit substrat de recevoir un liquide en lui permettant de s'étaler sur la surface la plus grande possible.For the purposes of the present invention, the term "tensioning agent" means an additive whose function is to lower and control the liquid surface energy of the composition (or surface tension). Surface energy is the energy required to bring the molecules of the liquid interior of the composition to its surface. The lower the surface energy of the composition, the greater the wettability of the surface of the metal substrate. Wettability is the ability for said substrate to receive a liquid allowing it to spread over the largest possible area.

L'énergie de surface de la composition est de préférence ajustée de façon à obtenir une bonne mouillabilité de la surface à revêtir dans des conditions de vitesse de ligne élevée avant que le produit ne soit figé en entrant dans la zone de séchage.The surface energy of the composition is preferably adjusted to obtain good wettability of the surface to be coated under high line speed conditions before the product is frozen upon entering the drying zone.

La composition de revêtement contient entre 0,01 et 1 % en poids d'un agent de tension, de préférence environ 0,1 % en poids d'un agent de tension.The coating composition contains between 0.01 and 1% by weight of a tensioning agent, preferably about 0.1% by weight of a tensioning agent.

On obtient ainsi avantageusement une composition de revêtement présentant une valeur de tension superficielle comprise entre 20 et 50 Dynes.cm-1 (20mN.m-1 et 50mN.m-1), de préférence entre 22 et 45 Dynes.cm-1' (22mN.m-1 et 45mN.m-1), plus préférentiellement entre 22 et 40 Dynes.cm-1 (22mN.m-1 et 40mN.m-1).Advantageously, a coating composition having a surface tension value of between 20 and 50 Dynes.cm -1 (20mN.m -1 and 50mNm -1 ), preferably between 22 and 45 Dynes.cm -1 ', is advantageously obtained. (22mN.m -1 and 45mN.m -1 ), more preferably between 22 and 40 Dynes.cm -1 (22mN.m -1 and 40mN.m -1 ).

L'agent de tension peut être ajouté séparément ou à l'occasion de l'incorporation d'un autre constituant contenant un tel agent, par exemple d'une dispersion ou d'une émulsion d'un polymère.The tensioning agent may be added separately or on the occasion of the incorporation of another component containing such an agent, for example a dispersion or an emulsion of a polymer.

A titre d'exemple d'agent de tension, on mentionnera les copolymères de polypropylèneglycol et de polyéthylèneglycol (tel que le Pluronic PE 3100®, fabriqué par B.A.S.F.), les résines à base de silicone (tel que le BYK348®, fabriqué par BYK), les glycols acétyléniques (tel que le Dyno1604®, fabriqué par Air Products), les mélanges anioniques et non ioniques (tel que le Dapro W95 HS®, commercialisé par Elementis), les ammoniums quaternaires (tel que le Cycloquart®, fabriqué par Clariant), les alcools polyéthoxylés modifiés (tel que le Triton DF16®, fabriqué par Union Carbide), ainsi que leurs mélanges compatibles.For example voltage agent may be mentioned polypropylene glycol and polyethylene glycol copolymers (such as Pluronic ® PE 3100 manufactured by BASF), silicone resins (such as ® BYK348, manufactured by BYK ), acetylenic glycols (such as Dyno1604 ® , manufactured by Air Products), anionic and nonionic mixtures (such as Dapro W95 HS ® , marketed by Elementis), quaternary ammoniums (such as Cycloquart ® , manufactured by Clariant), polyethoxylated alcohols modified (such as Triton ® DF16, manufactured by Union Carbide), and compatible mixtures thereof.

L'agent de tension peut être ajouté à la composition selon la présente invention sous la forme d'une solution aqueuse, d'une dispersion ou d'une émulsion dans l'eau, avec ou sans co-solvant.The tensioning agent can be added to the composition according to the present invention in the form of an aqueous solution, a dispersion or an emulsion in water, with or without a co-solvent.

Avantageusement, l'eau utilisée dans la composition de revêtement selon la présente invention subit au préalable un processus de déionisation de telle sorte que la conductivité de cette eau soit environ inférieure à 20µS/cm.Advantageously, the water used in the coating composition according to the present invention is first subjected to a deionization process such that the conductivity of this water is approximately less than 20 μS / cm.

Dans ces conditions de réalisation, le pH de la composition de revêtement pourra être un pH alcalin, de préférence compris entre 11 et 13, plus préférentiellement compris entre 11 et 12.Under these conditions, the pH of the coating composition may be an alkaline pH, preferably between 11 and 13, more preferably between 11 and 12.

Selon une caractéristique de l'invention, la composition de revêtement peut en outre contenir un polymère dont la fonction est d'abaisser la température de transition vitreuse du film sec de revêtement.According to one characteristic of the invention, the coating composition may further contain a polymer whose function is to lower the glass transition temperature of the dry coating film.

Lorsque ladite composition est appliquée sur un substrat et qu'elle subit ensuite une opération de séchage, la présence dudit polymère confère des propriétés d'élasticité et de souplesse au film sec de revêtement ainsi obtenu. Ledit polymère permet alors de diminuer ou d'éliminer l'apparition de craquelures au niveau du film sec de revêtement, lors d'une déformation mécanique ultérieure du substrat métallique.When said composition is applied to a substrate and subsequently undergoes a drying operation, the presence of said polymer imparts elasticity and flexibility properties to the dry film of coating thus obtained. Said polymer then makes it possible to reduce or eliminate the appearance of cracks in the dry coating film, during a subsequent mechanical deformation of the metal substrate.

A titre d'exemple dudit polymère, on mentionnera en particulier les polymères ou copolymères acryliques tels que le Polysol M-19® (fabriqué par SHOWA Highpolymer Co. Ltd.) ou le Rhodopas D-20 40® (fabriqué par Rhodia), les polyuréthanes, les alkydes, les esters d'époxy, ainsi que leurs mélanges compatibles.By way of example of said polymer, mention will in particular be made of acrylic polymers or copolymers such as Polysol M-19 ® (manufactured by SHOWA Highpolymer Co. Ltd.) or Rhodopas D-20 40 ® (manufactured by Rhodia), polyurethanes, alkyds, epoxy esters, as well as their compatible mixtures.

Avantageusement, ledit polymère peut être ajouté à la composition selon la présente invention sous la forme d'une dispersion ou d'une émulsion dans l'eau ou d'une solution aqueuse, en une proportion qui permet avantageusement d'atteindre jusqu'à 60% en poids du film sec de revêtement.Advantageously, said polymer can be added to the composition according to the present invention in the form of a dispersion or an emulsion in water or of an aqueous solution, in a proportion which advantageously allows to reach up to 60 % by weight of the dry coating film.

Sous cette forme, ledit polymère peut par la même occasion fournir à la composition l'agent de tension précédemment mentionné.In this form, said polymer can at the same time provide the composition with the previously mentioned tensioning agent.

Selon une autre caractéristique de l'invention, la composition de revêtement peut en outre contenir un additif permettant d'augmenter l'hydrophobicité du film sec de revêtement, en une proportion qui permet avantageusement d'atteindre jusqu'à 50% en poids du film sec de revêtement, de préférence jusqu'à 25% en poids du film sec de revêtement.According to another characteristic of the invention, the coating composition may furthermore contain an additive making it possible to increase the hydrophobicity of the dry coating film, in a proportion which advantageously makes it possible to attain up to 50% by weight of the film dry coating, preferably up to 25% by weight of the dry film coating.

Cet additif est avantageusement un silane, de préférence choisi parmi les di- ou triméthoxysilanes, ou les di- ou triéthoxysilanes fonctionnalisés, ainsi que leurs mélanges. La fonctionnalité organique peut être de type vinyl, aminé ou oxyrane (époxy). De préférence, le silane est choisi parmi les silanes à fonctionnalité époxy tel que le béta-(3,4-époxycyclohéxyl)éthyltriméthoxysilane, le 4-(triméthoxysilyl)butane-1,2 époxide ou le gamma-glycidoxypropyltriméthoxysilane.This additive is advantageously a silane, preferably chosen from di- or trimethoxysilanes, or functionalized di- or triethoxysilanes, as well as their mixtures. The organic functionality can be vinyl, amine or oxyrane (epoxy) type. Preferably, the silane is chosen from epoxy functional silanes such as beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 4- (trimethoxysilyl) 1,2-butane-epoxide or gamma-glycidoxypropyltrimethoxysilane.

Le silane peut également jouer le rôle d'un agent liant, d'un stabilisant pour la composition de revêtement et permettre d'augmenter la résistance à la corrosion du film sec de revêtement.The silane may also act as a binder, a stabilizer for the coating composition, and may increase the corrosion resistance of the dry coating film.

Ces silanes peuvent être utilisés indépendamment ou en combinaison sous forme préhydrolysée ou non.These silanes can be used independently or in combination in prehydrolysed form or not.

A l'introduction du silane peut aussi être associé l'ajout de Titanate ou Zirconate pour renforcer la réticulation du système liant en fonction des caractéristiques demandées au revêtement.At the introduction of the silane may also be associated with the addition of Titanate or Zirconate to enhance the crosslinking of the binder system depending on the characteristics required of the coating.

L'augmentation de l'hydrophobicité du film sec de revêtement peut s'observer visuellement, notamment lors de tests de corrosion cyclique (DIN 50017KTW), par la formation de gouttelettes de vapeur d'eau condensée (provenant de l'électrolyte) moins étalées que dans le cas d'un revêtement dont le liant est seulement composé de silicate.The increase in the hydrophobicity of the dry film coating can be observed visually, especially during cyclic corrosion tests (DIN 50017KTW), by the formation of condensed water vapor droplets (from the electrolyte) less spread than in the case of a coating whose binder is only composed of silicate.

On suppose que l'introduction du silane dans la composition de revêtement conduit à la diminution de la perméabilité et/ou de la porosité du film sec de revêtement à l'électrolyte, lui conférant ainsi son caractère hydrophobe.It is believed that the introduction of the silane into the coating composition leads to the decrease of the permeability and / or porosity of the dry film coating to the electrolyte, thereby conferring its hydrophobicity.

Le caractère hydrophobe du film sec de revêtement obtenu par l'introduction du silane dans la composition de revêtement permet d'appliquer une épaisseur de film sec plus faible pour un même résultat de résistance à la corrosion.The hydrophobicity of the dry coating film obtained by introducing the silane into the coating composition allows a lower dry film thickness to be applied for the same corrosion resistance result.

Selon une autre caractéristique de l'invention, la composition de revêtement peut en outre contenir un additif permettant de diminuer l'alcalinité libre de surface du film sec de revêtement, en une proportion qui permet avantageusement d'atteindre jusqu'à 25 % en poids du film sec de revêtement.According to another characteristic of the invention, the coating composition may furthermore contain an additive making it possible to reduce the free surface alkalinity of the dry coating film, in a proportion which advantageously makes it possible to attain up to 25% by weight. dry film coating.

Cet additif est de préférence un sel de Cérium (Ce), un sel de Lanthane (La), un sel de Molybdène (Mo), l'acide molybdique, l'acide paratoluène sulfonique, ainsi que leurs sels, ou bien un polyol tel que le glycérol, ainsi que leurs mélanges.This additive is preferably a cerium (Ce) salt, a Lanthanum salt (La), a molybdenum salt (Mo), molybdic acid, para-toluenesulphonic acid and their salts, or a polyol such as as glycerol, as well as their mixtures.

Selon une autre caractéristique de l'invention, la composition de revêtement peut en outre contenir un additif permettant d'augmenter les propriétés anticorrosion du film sec de revêtement, en une proportion qui permet avantageusement d'atteindre jusqu'à 25 % en poids du film sec de revêtement.According to another characteristic of the invention, the coating composition may furthermore contain an additive making it possible to increase the anticorrosion properties of the dry coating film, in a proportion which advantageously makes it possible to attain up to 25% by weight of the film dry coating.

Cet additif est de préférence un liant minéral tel qu'un titanate ou un zirconate, ainsi que leurs mélanges.This additive is preferably a mineral binder such as a titanate or a zirconate, and mixtures thereof.

Selon une autre caractéristique de l'invention, la composition de revêtement peut en outre contenir un agent lubrifiant. A titre d'exemple d'agent lubrifiant, on mentionnera en particulier des polymères organiques synthétiques tels que le polytétrafluoroéthylène, le polyéthylène, le polyéthylèneglycol ou des polymères organiques naturels tels que la cire de Carnauba ou les paraffines, ainsi que leurs mélanges. Le lubrifiant est ajouté à la composition de revêtement en une proportion qui permet avantageusement d'atteindre jusqu'à 15 % en poids du film sec de revêtement, de préférence entre 1,5 et 15 % en poids du film sec de revêtement, plus préférentiellement entre 3 et 15 % en poids du film sec de revêtement, encore plus préférentiellement entre 5 et 15 % en poids du film sec de revêtement.According to another characteristic of the invention, the coating composition may further contain a lubricating agent. As an example of a lubricating agent, mention will in particular be made of synthetic organic polymers such as polytetrafluoroethylene, polyethylene, polyethylene glycol or natural organic polymers such as carnauba wax or paraffins, as well as mixtures thereof. The lubricant is added to the coating composition in a proportion which advantageously makes it possible to attain up to 15% by weight of the dry coating film, preferably between 1.5 and 15% by weight of the dry coating film, more preferably between 3 and 15% by weight of the dry coating film, more preferably between 5 and 15% by weight of the dry coating film.

Dans la pratique, il s'est avéré que le lubrifiant puisse nécessiter un stabilisant afin d'éviter une séparation de phases dans la composition de revêtement.In practice, it has been found that the lubricant may require a stabilizer to avoid phase separation in the coating composition.

A titre d'exemple de stabilisant, on mentionnera en particulier, les argiles organophiles (naturelles ou synthétiques), les dérivés de silice, les dérivés cellulosiques, la gomme de xanthane ou les épaississants associatifs de type polyuréthane ou acrylique, ainsi que leurs mélanges.As an example of stabilizer, mention will be made in particular, organophilic clays (natural or synthetic), silica derivatives, cellulose derivatives, xanthan gum or associative thickeners of polyurethane or acrylic type, and mixtures thereof.

De façon avantageuse, le stabilisant est ajouté à la composition de revêtement selon la présente invention en une proportion qui permet d'atteindre entre environ 0,1 et 5 % en poids du film sec de revêtement.Advantageously, the stabilizer is added to the coating composition according to the present invention in a proportion which achieves between about 0.1 and 5% by weight of the dry coating film.

Selon une autre caractéristique de l'invention, la composition de revêtement peut en outre être additionnée d'un agent anti-mousse choisi de façon compatible avec les autres constituants de la composition de revêtement et dont la quantité optimale est déterminée selon les expérimentations classiques de routine connues de l'homme du métier.According to another characteristic of the invention, the coating composition may additionally be added with an antifoam agent chosen in a manner compatible with the other constituents of the coating composition and the optimal amount of which is determined according to the conventional experiments of routines known to those skilled in the art.

Dans les conditions de réalisation de la composition selon la présente invention, ladite composition pourra être essentiellement dépourvue de solvant organique. En effet, les solvants organiques se sont avérés, dans la pratique, peu compatibles avec les silicates de sodium et/ou de potassium et/ou de lithium, constituants principaux de la composition de revêtement.Under the conditions for producing the composition according to the present invention, said composition may be substantially free of organic solvent. Indeed, organic solvents have been found, in practice, to be incompatible with sodium and / or potassium and / or lithium silicates, the main constituents of the coating composition.

La présente invention se rapporte également à un procédé de revêtement d'un substrat métallique qui comprend l'application de la composition de revêtement préalablement décrite sur la surface dudit substrat.The present invention also relates to a method of coating a metal substrate which comprises applying the previously described coating composition to the surface of said substrate.

Dans le cadre de la présente invention, l'application de la composition de revêtement préalablement décrite est réalisée au cours d'une opération qui consiste à déposer un film humide de ladite composition, de faible épaisseur appropriée, suivie d'une opération de séchage dudit substrat métallique ainsi revêtu, donnant naissance à un film sec de revêtement dudit substrat.In the context of the present invention, the application of the coating composition described above is carried out during an operation which consists in depositing a wet film of said composition, of suitable low thickness, followed by a drying operation of said composition. metal substrate thus coated, giving rise to a dry coating film of said substrate.

Avantageusement, l'épaisseur de film humide de la composition de revêtement déposé sur le substrat métallique est comprise entre 0,3 et 39 µm, de préférence comprise entre 0,3 et 30 µm et le film humide est appliqué à raison de 0,6 à 40 g/m2, de préférence de 0,6 à 24 g/m2.Advantageously, the wet film thickness of the coating composition deposited on the metal substrate is between 0.3 and 39 μm, preferably between 0.3 and 30 μm and the wet film is applied at a rate of 0.6 at 40 g / m 2 , preferably from 0.6 to 24 g / m 2 .

Le procédé objet de la présente invention peut être réalisé en ligne, après l'étape de revêtement métallique de zinc ou d'alliage à base de zinc du substrat en acier, ou sur ligne de reprise telle que sur ligne de pré-laquage (« coil-coating »).The method which is the subject of the present invention can be carried out online, after the metal coating step of zinc or zinc-based alloy of the steel substrate, or on a recovery line such as on a pre-lacquering line (" coil-coating ").

Conformément au procédé objet de la présente invention, l'opération de dépôt du film humide de la composition de revêtement sur le substrat métallique peut être avantageusement effectuée par pulvérisation, par aspersion suivie d'une opération d'essorage, par trempage suivi d'une opération d'essorage ou au moyen d'un système d'enduction composé d'au moins un rouleau.According to the method that is the subject of the present invention, the operation of depositing the wet film of the coating composition on the metal substrate can advantageously be carried out by spraying, spraying followed by a spinning operation, by soaking followed by spinning operation or by means of a coating system composed of at least one roller.

Dans le cas de l'aspersion ou du trempage, l'opération d'essorage permet de contrôler l'épaisseur du film humide déposé sur le substrat métallique. Cette opération d'essorage peut être avantageusement réalisée à l'aide d'un jeu de rouleaux essoreurs.In the case of spraying or soaking, the spinning operation makes it possible to control the thickness of the wet film deposited on the metal substrate. This spinning operation can be advantageously carried out using a set of spinning rolls.

Dans un mode de réalisation avantageux de la présente invention, l'opération de séchage du substrat métallique revêtu du film humide est réalisée par chauffage du substrat métallique ou du film humide de manière à porter ces derniers à une température comprise entre la température ambiante et 240°C. L'opération de chauffage peut être réalisée directement par induction, ou indirectement par convection ou par infra rouge. Le chauffage par convection requiert en général une durée de séchage plus longue qu'un chauffage par induction ou par infrarouge. Cette opération de séchage est avantageusement réalisée par chauffage du substrat métallique ou du film humide de manière à porter ces derniers de préférence à une température d'au moins environ 35°C pendant une durée d'au moins 2 secondes si on utilise un chauffage par convection et pendant une durée maximale de 10 secondes, de préférence de 5 secondes, plus préférentiellement de 1 à 2 secondes, si on utilise un chauffage par induction ou par infrarouge.In an advantageous embodiment of the present invention, the drying operation of the metal substrate coated with the wet film is carried out by heating the metal substrate or the wet film so as to bring the latter to a temperature of between room temperature and room temperature. ° C. The heating operation can be performed directly by induction, or indirectly by convection or infrared. Convection heating generally requires a longer drying time than induction heating or infrared heating. This drying operation is advantageously carried out by heating the metal substrate or the wet film so as to bring the latter preferably to a temperature of at least about 35 ° C for a period of at least 2 seconds if heating is used. convection and for a maximum of 10 seconds, preferably 5 seconds, more preferably 1 to 2 seconds, if using induction heating or infrared heating.

Avantageusement, l'opération de séchage est conduite afin d'obtenir une épaisseur de film sec de revêtement comprise entre 0,05 et 0,80 µm, de préférence entre 0,05 et 0,60 µm et de façon à obtenir un poids de couche de film sec de revêtement compris entre 0,1 g/m2 et 1,3 g/m2, de préférence entre 0,2 g/m2 et 1,2 g/m2, plus préférentiellement entre 0,2 et 0,5 g/m2.Advantageously, the drying operation is carried out in order to obtain a dry film thickness of coating of between 0.05 and 0.80 μm, preferably between 0.05 and 0.60 μm and so as to obtain a weight of layer of dry film coating between 0.1 g / m 2 and 1.3 g / m 2 , preferably between 0.2 g / m 2 and 1.2 g / m 2 , more preferably between 0.2 and 0.5 g / m 2 .

Selon un exemple particulier du procédé objet de la présente invention, les opérations de dépôt du film humide et de séchage sont réalisées entre les opérations de revêtement métallique à base de zinc ou d'alliage de zinc du substrat en acier et de bobinage final.According to a particular example of the method which is the subject of the present invention, the operations of deposition of the wet film and of drying are carried out between the operations of metal coating based on zinc or zinc alloy of the steel substrate and final winding.

La présente invention se rapporte également aux diverses utilisations de la composition de revêtement objet de la présente invention.The present invention also relates to the various uses of the coating composition object of the present invention.

Selon une caractéristique de la présente invention, la composition de revêtement peut être utilisée en tant que couche de protection anti-corrosion de tôles métalliques lorsqu'elle est appliquée sur lesdites tôles. Avantageusement, ladite composition peut être utilisée en tant que couche de protection anti-corrosion de tôles métalliques destinées à être temporairement stockées.According to a feature of the present invention, the coating composition can be used as a corrosion protection layer of metal sheets when it is applied to said sheets. Advantageously, said composition may be used as an anti-corrosion protection layer for metal sheets intended to be temporarily stored.

Lorsque ladite composition de revêtement est appliquée sur un substrat métallique que l'on fait passer dans des bains de dégraissage, comme par exemple au cours d'une gamme peinture automobile, la résistance chimique de la couche de revêtement obtenue dépend de multiples paramètres, dont notamment :

  • les conditions de séchage dudit substrat revêtu du film humide lors du procédé d'application de la composition de revêtement,
  • la température et l'alcalinité des bains de dégraissage, ou
  • le temps d'immersion du substrat dans les bains de dégraissage.
When said coating composition is applied to a metal substrate which is passed through degreasing baths, as for example during a car paint range, the chemical resistance of the coating layer obtained depends on multiple parameters, including especially :
  • the drying conditions of said wet-film-coated substrate during the coating composition application process,
  • the temperature and alkalinity of the degreasing baths, or
  • the immersion time of the substrate in the degreasing baths.

Par exemple, lors des bains de dégraissage d'une gamme peinture automobile, une couche de film de revêtement sec selon la présente invention, lorsqu'elle a été appliquée sur un substrat métallique puis séchée à 240°C, résiste complètement aux dits bains de dégraissage. En revanche, lorsqu'elle a été séchée à 145°C, ladite couche de film de revêtement sec est partiellement solubilisée par les bains de dégraissage et lorsqu'elle a été séchée à 50°C, elle est complètement solubilisée par les bains de dégraissage.For example, in the degreasing baths of an automobile paint range, a layer of dry coating film according to the present invention, when it has been applied to a metal substrate and then dried at 240 ° C., completely resists said soak baths. degreasing. On the other hand, when it has been dried at 145 ° C., said layer of dry coating film is partially solubilized by the degreasing baths and when it has been dried at 50 ° C., it is completely solubilized by the degreasing baths. .

Avantageusement, la composition de revêtement peut être utilisée en tant que couche de lubrification lorsqu'elle contient en outre un agent lubrifiant et qu'elle est appliquée sur des tôles métalliques en vue de leur mise en forme, en particulier en vue du pliage, du cintrage et de l'emboutissage desdites tôles métalliques.Advantageously, the coating composition can be used as a lubricating layer when it further contains a lubricant and is applied to metal sheets for shaping, particularly for folding, bending and stamping said metal sheets.

Selon une autre caractéristique de la présente invention, la composition de revêtement peut être utilisée en tant qu'agent anti-empreintes digitales (« anti-fingerprint »). Dans la pratique, on a pu observer que des tôles métalliques recouvertes de la composition de revêtement objet de la présente invention peuvent être manipulées telles quelles, sans que des traces de doigts restent ultérieurement imprimées sur lesdites tôles métalliques.According to another characteristic of the present invention, the coating composition may be used as an anti-fingerprint agent. In practice, it has been observed that metal sheets coated with the coating composition which is the subject of the present invention can be handled. as such, without fingerprints remaining subsequently printed on said metal sheets.

Selon une autre caractéristique de la présente invention, la composition de revêtement peut être appliquée sur des pièces de substrat métallique destinées à être soudées.According to another characteristic of the present invention, the coating composition may be applied to metal substrate parts to be welded.

Dans le cas où des films de revêtement de faible épaisseur sont appliqués, lesdits substrats ainsi revêtus conservent leur propriété de soudabilité et les opérations de soudage peuvent se faire directement.In the case where thin coating films are applied, said substrates thus coated retain their weldability property and the welding operations can be done directly.

Dans le cas où le film de revêtement est d'épaisseur plus importante, la composition de revêtement peut nécessiter l'ajout de pigments conducteurs tels que le phosphure de fer, le silicate d'ammonium, le nickel, le tungstène, le zinc (pur ou allié) et le carbone, ainsi que leurs mélanges.In the case where the coating film is of greater thickness, the coating composition may require the addition of conductive pigments such as iron phosphide, ammonium silicate, nickel, tungsten, zinc (pure or alloyed) and carbon, as well as their mixtures.

D'autres caractéristiques et avantages de la présente invention apparaîtront à la lumière des exemples ci-après. Ces exemples sont donnés à titre indicatif et non limitatif.Other features and advantages of the present invention will become apparent in light of the examples below. These examples are given for information only and not limiting.

Exemple 1: Composition de revêtement à base de silicate de sodium (A)Example 1: Sodium silicate coating composition (A)

Dans la composition de revêtement (A) formulée ci-après, on utilise :

  • la solution de silicate de sodium (20N32®, fabriquée par Rhodia) répondant à la composition pondérale suivante :
    • SiO2    28,6 % en poids
    • Na2O    8,9 % en poids
    • Na2CO3    0,1 % en poids
    • eau    qsp 100% en poids
  • l'agent de tension : Copolymère de polypropylèneglycol et de polyéthylèneglycol avec 10% de polyéthylèneglycol dans la molécule (Pluronic PE 3100® fabriqué par B.A.S.F.).
In the coating composition (A) formulated below, use is made of:
  • the sodium silicate solution (20N32 ®, manufactured by Rhodia) having the following composition by weight:
    • SiO 2 28.6% by weight
    • Na 2 O 8.9% by weight
    • Na 2 CO 3 0.1% by weight
    • water qs 100% by weight
  • tensioning agent: Copolymer of polypropylene glycol and polyethylene glycol with 10% polyethylene glycol in the molecule (Pluronic PE 3100 ® manufactured by BASF).

Dans un bécher de 5 litres, équipé d'un disperseur Rayneri® de type 33/300 et d'une turbine défloculeuse de diamètre 85 mm, introduire 1463,6 g d'eau déionisée, ajouter sous agitation (vitesse 250 t/min) 4 g de Pluronic PE 3100®, laisser mélanger 10 minutes à 350 t/min, ajouter sous agitation (vitesse 250 t/min) 2 532,4 g de solution de silicate de sodium (20N32®) et laisser mélanger 30 minutes à 350 t/min. Composition de revêtement (A) % massique Silicate de sodium 23,7 Agent de tension 0,1 Eau 76,2 In a 5-liter beaker, equipped with a Rayneri ® 33/300 type disperser and a 85 mm diameter deflocculating turbine, introduce 1463.6 g of deionized water, add with stirring (speed 250 rpm) 4 g of Pluronic PE 3100 ® , allow to mix 10 minutes at 350 rpm, add with stirring (speed 250 rpm) 2532.4 g of sodium silicate solution (20N32 ® ) and allow to mix 30 minutes at 350 rpm. Coating composition (A) % mass Sodium silicate 23.7 Agent of tension 0.1 Water 76.2

Exemple 2: Composition de revêtement lubrifié à base de silicate de sodium (B)Example 2 Lubricated Sodium Silicate Coating Composition (B)

Dans la composition de revêtement (B) formulée ci-après, on utilise:

  • la solution de silicate de sodium 20N32® utilisée à l'exemple 1 dans la composition (A),
  • une émulsion dans l'eau à 45% en poids de matière sèche de polymère acrylique Polysol M-19®, fabriqué par SHOWA Highpolymer Co. Ltd,
  • une émulsion dans l'eau à 45% en poids de matière sèche de polyéthylène MICHEM® Emulsion 45745, fabriqué par MICHELMAN,
  • une dispersion dans l'eau à 41 % en poids de matière sèche de polytétrafluoroéthylène MICHEM® Glide 5, fabriqué par MICHELMAN.
In the coating composition (B) formulated below, use is made of:
  • the sodium silicate solution 20N32 ® used in Example 1 in the composition (A),
  • an emulsion in water at 45% by weight of Polysol M-19 ® acrylic polymer solids, manufactured by SHOWA Highpolymer Co. Ltd,
  • an emulsion in water at 45% by weight of polyethylene dry matter MICHEM ® Emulsion 45745, manufactured by MICHELMAN,
  • a dispersion in water at 41% by weight of dry matter of polytetrafluoroethylene MICHEM ® Glide 5, manufactured by MICHELMAN.

Dans un pot plastique de 0,8 litre équipé d'un disperseur Rayneri® de type 33/300 et d'une turbine défloculeuse de diamètre 55 mm, introduire 385,3 g d'eau déionisée, ajouter sous agitation faible (vitesse 250 t/min) 14,9 g de Polysol M-19®, mélanger 5 minutes, ajouter sous agitation faible (vitesse 250 t/min) 17,2 g de MICHEM® Emulsion 45745, mélanger 5 minutes, ajouter sous agitation faible (vitesse 250 t/min) 9,7 g de MICHEM® Glide 5, mélanger 5 minutes, ajouter sous agitation faible (vitesse 250 t/min) 172,9 g de solution de silicate de sodium (20N32®) puis laisser mélanger 30 minutes sous faible agitation (vitesse 250 t/min). Composition de revêtement lubrifié (B) % massique Silicate de sodium 10,8 Polytétrafluoroéthylène (PTFE) 0,7 Polyéthylène (PE) 1,3 Polymère acrylique 1,1 Eau 86,1 Composition du film sec de revêtement lubrifié (B) % massique Silicate de sodium 78 Polymère acrylique 8 PTFE et PE 14 In a 0.8 liter plastic jar equipped with a Rayneri ® type 33/300 disperser and a 55 mm diameter deflocculating turbine, introduce 385.3 g of deionized water, add with low stirring (250 t speed). / min) 14.9 g of Polysol M-19 ® , mix for 5 minutes, add with low stirring (speed 250 rpm) 17.2 g of MICHEM ® Emulsion 45745, mix for 5 minutes, add with low stirring (speed 250 t / min) 9.7 g of MICHEM ® Glide 5, mix for 5 minutes, add with low stirring (speed 250 rpm) 172.9 g of sodium silicate solution (20N32 ® ) and allow to mix for 30 minutes under low stirring (speed 250 rpm). Lubricated coating composition (B) % mass Sodium silicate 10.8 Polytetrafluoroethylene (PTFE) 0.7 Polyethylene (PE) 1.3 Acrylic polymer 1.1 Water 86.1 Composition of lubricated dry coating film (B) % mass Sodium silicate 78 Acrylic polymer 8 PTFE and PE 14

Exemple 3: Composition de revêtement à base de silicate de potassium (C)Example 3: Potassium silicate coating composition (C)

Dans la composition de revêtement (C) formulée ci-après, on utilise :

  • la solution de silicate de potassium (K4/2®, fabriqué par CLARIANT) répondant à la composition pondérale suivante:
    • SiO2    26,5 % en poids
    • K2O    12,9 % en poids
    • eau    qsp 100 % en poids
  • l'agent de tension Pluronic PE 3100® utilisé à l'exemple 1 dans la composition (A).
In the coating composition (C) formulated below, use is made of:
  • the potassium silicate solution (K4 / 2 ® , manufactured by CLARIANT) having the following weight composition:
    • SiO 2 26.5% by weight
    • K 2 O 12.9% by weight
    • water qs 100% by weight
  • the Pluronic PE 3100 ® tensioning agent used in Example 1 in the composition (A).

Dans un bécher de 5 litres équipé d'un disperseur Rayneri de type 33/300 et d'une turbine défloculeuse de diamètre 85 mm, introduire 1535,2 g d'eau déionisée, ajouter sous agitation (vitesse 250 t/min) 4 g de Pluronic PE 3100®, laisser mélanger 10 minutes à 350 t/min, ajouter sous agitation (vitesse 250 t/min) les 2460,8 g de solution de silicate de potassium K4/2® puis laisser mélanger 30 minutes à 350 t/min. Composition de revêtement (C) % massique Silicate de potassium 24,2 Agent de tension 0,1 Eau 75,7 In a 5-liter beaker equipped with a Rayneri type 33/300 disperser and a 85 mm diameter deflocculating turbine, introduce 1535.2 g of deionized water, add with stirring (speed 250 rpm) 4 g of Pluronic PE 3100 ® , let mix for 10 minutes at 350 rpm, add with stirring (speed 250 rpm) the 2460.8 g of potassium silicate solution K4 / 2 ® then let mix 30 minutes at 350 t / min. Coating composition (C) % mass Potassium silicate 24.2 Agent of tension 0.1 Water 75.7

Exemple 4: Composition de revêtement à base de silicate de lithium (D)Example 4 Lithium Silicate Coating Composition (D)

Dans la composition de revêtement (D) formulée ci-après, on utilise :

  • la solution de silicate de lithium (KLEBOFON 3®, fabriqué par CLARIANT) répondant à la composition pondérale suivante:
    • SiO2    21 % en poids
    • Li2O    2,9 % en poids
    • eau    qsp 100% en poids
In the coating composition (D) formulated below, use is made of:
  • the lithium silicate solution (KLEBOFON 3 ® , manufactured by CLARIANT) having the following weight composition:
    • SiO 2 21% by weight
    • Li 2 O 2.9% by weight
    • water qs 100% by weight

Dans un bécher de 5 litres équipé d'un disperseur Rayneri de type 33/300 et d'une turbine défloculeuse de diamètre 85 mm, introduire 596 g d'eau déionisée, ajouter sous agitation (vitesse 250 t/min) 4 g de Pluronic PE 3100®, laisser mélanger 10 minutes à 350 t/min, ajouter sous agitation (vitesse 250 t/min) les 3400 g de solution de silicate de lithium KLEBOFON 3®. Composition de revêtement (D) % massique Silicate de lithium 20,3 Agent de tension 0,1 Eau 79,6 In a 5-liter beaker equipped with a Rayneri 33/300 type disperser and a 85 mm diameter deflocculating turbine, introduce 596 g of deionized water, add with stirring (250 rpm speed) 4 g of Pluronic PE 3100 ® , let mix for 10 minutes at 350 rpm, add with stirring (speed 250 rpm) the 3400 g of KLEBOFON 3 ® lithium silicate solution. Coating composition (D) % mass Lithium silicate 20.3 Agent of tension 0.1 Water 79.6

Exemple 5: Energie de surface de la composition de revêtement en fonction de l'agent de tensionExample 5: Surface energy of the coating composition as a function of the tensioning agent

Ces tests de détermination d'énergie de surface ont été réalisés selon les normes DIN53914 ou ASTM D 971 (test selon Du Noüy).These surface energy determination tests were performed according to DIN53914 or ASTM D 971 (test according to Du Noüy).

Les tests de mesure de l'énergie de surface dont les résultats sont regroupés dans le tableau ci-dessous ont été réalisés à partir de la solution de silicate de sodium (20N32®) utilisée à l'exemple 1, à laquelle différents agents de tension ont été ajoutés. Agent de tension % massique Tension de surface (dynes/cm) Solution (20N32®) - 0 42-45 Solution (20N32®) + Agent de tension Copolymère de polypropylèneglycol et de polyéthylèneglycol non ionique (Pluronic PE 3100®, fabriqué par B.AS.F.) 0,1 - 0,5 36 - 38 Solution (20N32®) + Agent de tension Polyéther modifié silicone (BYK 348®, fabriqué par BYK) 0,1-0,5 22-23 Solution (20N32®) + Agent de tension Glycol acétylénique non ionique (Dynol® 604, fabriqué par AIR PRODUCTS) 0,1 27-28 Solution (20N32®) + Agent de tension Mélange anionique et non ionique (Dapro W95HS® commercialisé par ELEMENTIS) 0,1 27 - 29 Solution (20N32®) + Agent de tension Ammonium quaternaire (Cycloquart® fabriqué par CLARIANT) 0,4 36-38 Solution (20N32®) + Agent de tension Alcool polyéthoxylé modifié non ionique (Triton DF 16® fabriqué par UNION CARBIDE) 0,1 32 - 33 The tests for measuring the surface energy and the results are summarized in Table below were produced from the sodium silicate solution (20N32 ®) used in Example 1, to which different voltage agents have been added. Agent of tension % mass Surface tension (dynes / cm) Solution (20N32 ® ) - 0 42-45 Solution (20N32 ® ) + Tension Agent Copolymer of polypropylene glycol and nonionic polyethylene glycol (Pluronic PE 3100 ® , manufactured by B.AS.F.) 0.1 - 0.5 36 - 38 Solution (20N32 ® ) + Tension Agent Silicone Modified Polyether (BYK 348 ® , manufactured by BYK) 0.1-0.5 22-23 Solution (20N32 ® ) + Tension Agent Nonionic Acetylenic Glycol (Dynol ® 604, manufactured by AIR PRODUCTS) 0.1 27-28 Solution (20N32 ® ) + Tension Agent Anionic and nonionic mixture (Dapro W95HS ® marketed by ELEMENTIS) 0.1 27 - 29 Solution (20N32 ® ) + Tension Agent Quaternary ammonium (Cycloquart ® manufactured by CLARIANT) 0.4 36-38 Solution (20N32 ® ) + Tension Agent Nonionic modified polyethoxylated alcohol (Triton DF 16 ® manufactured by UNION CARBIDE) 0.1 32 - 33

Exemple 6: Tests de lubrification et de corrosionExample 6: Lubrication and Corrosion Tests 6-1) Tests de lubrification6-1) Lubrication tests

Ces tests ont été réalisés sur des échantillons de substrat métallique revêtus d'une composition selon la présente invention répondant à la composition suivante (% exprimés en poids de matière sèche par rapport au film sec de revêtement obtenu):

  • 78% de silicate de sodium (à partir de la solution de silicate de sodium 20N32® de l'exemple 1),
  • 8% de polymère acrylique (émulsion dans l'eau à 45% en poids de matière sèche de polymère acrylique Polysol M-19®, fabriqué par SHOWA Highpolymer Co. Ltd),
  • 14% d'agent lubrifiant, dont on fait varier la nature et la composition comme décrit dans le tableau ci-dessous.
These tests were carried out on metal substrate samples coated with a composition according to the present invention corresponding to the following composition (% expressed by weight of dry matter relative to the dry film of coating obtained):
  • 78% sodium silicate (from the sodium silicate solution 20N32 ® of Example 1)
  • 8% of acrylic polymer (emulsion in water at 45% by weight of Polysol M-19 ® acrylic polymer solids, manufactured by SHOWA Highpolymer Co. Ltd),
  • 14% lubricating agent, the nature and composition of which are varied as described in the table below.

Le test consiste à soumettre l'échantillon de substrat métallique à un frottement sur une longueur d'environ 50 mm (voir figure 1).The test consists of subjecting the metal substrate sample to a friction over a length of about 50 mm (see FIG. figure 1 ).

Les échantillons sont d'un format de 50 mm x 200 mm et sont traités sur les 2 faces.The samples have a size of 50 mm x 200 mm and are processed on both sides.

Une force latérale (FL) est imposée à l'échantillon et celui-ci est soumis à une traction à vitesse constante de 20 mm/min. La force de traction FT est mesurée après une distance de frottement de 50 mm.A lateral force (F L ) is imposed on the sample and it is subjected to a constant speed pull of 20 mm / min. The tensile force F T is measured after a friction distance of 50 mm.

La valeur de coefficient de frottement est exprimée par le rapport: Coefficient de frottement μ = force de traction 2 x force latérale = F T 2 ⁢ F L

Figure imgb0001
The coefficient of friction value is expressed by the ratio: Coefficient of friction μ = tractive force 2 x lateral force = F T 2 ⁢ F The
Figure imgb0001

Ce test permet de déterminer la qualité de lubrification des films de revêtement testés. Plus la valeur de µ est faible et plus la lubrification est bonne.This test makes it possible to determine the quality of lubrication of the coating films tested. The lower the μ value, the better the lubrication.

La température de mesure est de 21 ± 2° C.The measurement temperature is 21 ± 2 ° C.

Les poids de couche de film sec de revêtement déposé sur les échantillons de substrat métallique sont compris entre 1 et 1,2 g/m2.The coating dry film layer weights deposited on the metal substrate samples are between 1 and 1.2 g / m 2 .

Les mesures reportées dans le tableau ci-dessous ont été obtenues pour une force latérale FL de 500 daN.The measurements reported in the table below were obtained for a lateral force F L of 500 daN.

L'échantillon de référence est une tôle électrozinguée (7,5 µm sur chaque face) sur laquelle une couche d'huile ANTICORRIT 4107 S® (fabricant FUCHS) à été appliquée à hauteur de 2,5 g/m2 sur chacune des faces. Cette huile est largement utilisée dans l'industrie automobile en tant que lubrifiant de tôles destinées à l'emboutissage. Composition du film sec de revêtement Composition de l'agent lubrifiant contenu dans la composition du film sec de revêtement (pourcentages exprimés en poids de matière sèche) µ (B1) 75% PTFE 0,18 25% PEG (B2) 50% PTFE 0,176 50% PEG (B3) 25% PTFE 0,177 25% PEG 50% PE (B4) 17% PTFE 0,169 50% PEG 33% PE (B5) 34% PTFE 0,178 66%PE (B6) 100% PEG 0,203 Echantillon de référence - 0,425 PTFE = Polytétrafluoroéthylène
PEG = Polyéthylène glycol
PE = Polyéthylène The reference sample is an electrogalvanised sheet (7.5 μm on each side) on which a layer of ANTICORRIT 4107 S ® oil (manufacturer FUCHS) has been applied at a height of 2.5 g / m 2 on each face . This oil is widely used in the automotive industry as a lubricant for sheet metal for stamping. Composition of dry coating film Composition of the lubricating agent contained in the composition of the dry coating film (percentages expressed by weight of dry matter) μ (B1) 75% PTFE 0.18 25% PEG (B2) 50% PTFE 0.176 50% PEG (B3) 25% PTFE 0.177 25% PEG 50% PE (B4) 17% PTFE 0.169 50% PEG 33% PE (B5) 34% PTFE 0.178 66% PE (B6) 100% PEG 0.203 Reference sample - 0,425 PTFE = Polytetrafluoroethylene
PEG = Polyethylene glycol
PE = Polyethylene

Les coefficients de frottement des échantillons revêtus d'un film sec de composition selon la présente invention (B1) à (B6) sont inférieurs au coefficient de frottement de l'échantillon de référence. Ceci indique que la lubrification des échantillons revêtus d'un film sec de composition selon la présente invention (B1) à (B6) est meilleure que celle de l'échantillon de référence.The coefficients of friction of the samples coated with a dry film of composition according to the present invention (B1) to (B6) are lower than the coefficient of friction of the reference sample. This indicates that lubrication of the dry film-coated samples of the present invention (B1) to (B6) is better than that of the reference sample.

6-2) Tests de corrosion6-2) Corrosion tests 6-2-1)6-2-1) Tests de corrosion accéléréeAccelerated corrosion tests

Echantillon d'acier galvanisé à chaud (10 µm) de référenceSample hot-dip galvanized steel (10 μm) Echantillon d'acier galvanisé à chaud (10µm) revêtu d'un film sec de revêtement selon la composition (A) avec un poids de couche égal à :Sample of hot-dip galvanized steel (10 μm) coated with a dry film of coating according to composition (A) with a weight of layer equal to: 0,3 g/m2 0.3 g / m 2 0,6 g/m2 0.6 g / m 2 0,9 g/m2 0.9 g / m 2 1,2 g/m2 1.2 g / m 2 Test d'humidotherme (durée 15 cycles) réalisé selon la norme DIN 50017Humidotherm test (duration 15 cycles) performed according to DIN 50017 Rouille blanche sur 100% de la surface (après 5 cycles seulement)White rust on 100% of the surface (after 5 cycles only) Modification de l'aspect : Rouille blanche sur 70% de la surfaceChange in appearance: White rust on 70% of the surface Pas de modification d'aspectNo appearance changes Pas de modification d'aspectNo appearance changes Pas de modification d'aspectNo appearance changes Test de brouillard salin (durée 48 heures) réalisé selon la norme ISO 9227Salt spray test (48 hours duration) according to ISO 9227 Rouille blanche sur 100% de la surface (après 24 heures seulement)White rust on 100% of the surface (after 24 hours only) Rouille blanche sur 60% de la surfaceWhite rust on 60% of the surface Rouille blanche sur 20% de la surfaceWhite rust on 20% of the surface Rouille blanche sur moins de 5% de la surfaceWhite rust on less than 5% of the surface Pas de modification d'aspectNo appearance changes

6-2-2)6-2-2) Tests de corrosion naturelleNatural corrosion tests

Ces tests ont consisté à exposer des échantillons galvanisés aux intempéries naturelles dans un environnement extérieur industriel. Echantillon d'acier galvanisé à chaud (10 µm) de référence Echantillon d'acier galvanisé à chaud (10 µm) revêtu d'un film sec de revêtement selon la composition (A) avec un poids de couche compris entre 0,6 et 0,9 g/m2 Durée d'exposition extérieure : 6 mois Modification de l'aspect : Rouille blanche sur 100% de la surface Pas de modification d'aspect Durée d'exposition extérieure : 9 mois Modification de l'aspect : Rouille blanche amplifiée sur 100% de la surface Modification d'aspect faible (léger ternissement) These tests consisted of exposing galvanized samples to natural weather in an industrial outdoor environment. Sample hot-dip galvanized steel (10 μm) Sample of hot-dip galvanized steel (10 μm) coated with a dry coating film according to composition (A) with a coating weight of between 0.6 and 0.9 g / m 2 Duration of outdoor exposure: 6 months Change in appearance: White rust on 100% of the surface No appearance changes Duration of outdoor exposure: 9 months Modification of the appearance: White rust amplified on 100% of the surface Low aspect modification (slight tarnishing)

Exemple 7 : Résultats d'une formulation comprenant un silaneExample 7 Results of a Formulation Comprising a Silane Composition du revêtement (E)Composition of the coating (E) % massique% mass silicate de sodium 20N32® sodium silicate 20N32 ® 29,729.7 silane = gamma glycidoxypropyltriméthoxysilanesilane = gamma glycidoxypropyltrimethoxysilane 3,733.73 Pluronic PE 3100® Pluronic PE 3100 ® 0,070.07 EauWater 66,566.5

Test de corrosion (DIN 50017 KTW) :Corrosion test (DIN 50017 KTW):

Test : DIN 50017KTW (20 cycles)Test: DIN 50017KTW (20 cycles) Substrat en acier galvanisé à chaud (10 µm) revêtu d'un film sec de revêtement selon la composition (A) ou (E) avec un poids de couche de:Hot-dip galvanized steel substrate (10 μm) coated with a dry coating film according to composition (A) or (E) with a coating weight of: 0,2 g/m2 0.2 g / m 2 0, 5 g/m2 0, 5 g / m 2 0,65 g/m2 0.65 g / m 2 Formulation (A)Formulation (A) Modification de l'aspect : rouille blanche sur 90% de la surfacéChange in appearance: white rust on 90% of the surface Modification de l'aspect: rouille blanche sur 50% de la surfaceChange in appearance: white rust on 50% of the surface Très légère modification de l'aspect: rouille blanche sur 15% de la surfaceVery slight change in appearance: white rust on 15% of the surface Formulation (E)Formulation (E) Très légère modification de l'aspect : rouille blanche sur 20% de la surfaceVery slight change in appearance: white rust on 20% of the surface Pas de modification de l'aspectNo change in appearance Pas de modification de l'aspectNo change in appearance

Ces résultats montrent que la composition comprenant le silane est plus performante contre la corrosion que la composition sans silane. L'introduction de silane permet donc de diminuer les poids de couche tout en maintenant les mêmes propriétés anticorrosion.These results show that the composition comprising the silane is more effective against corrosion than the silane-free composition. The introduction of silane thus makes it possible to reduce the weight of the layer while maintaining the same anticorrosion properties.

Claims (23)

Composition de revêtement de substrat métallique présentant une surface extérieure libre constituée par une couche de zinc ou d'alliage à base de zinc, caractérisée en ce qu'elle comprend (% en poids): - silicate(s) de lithium introduits sous forme de solution aqueuse    3 % - 35 % - agent de tension    0,01 %-1% - un silane, en une proportion qui permet d'atteindre jusqu'à 50 % en poids du film sec de revêtement, - eau    qsp 100 % ladite composition ayant un pH compris entre 11 et 13, avantageusement entre 11 et 12.A metal substrate coating composition having a free outer surface formed by a layer of zinc or zinc-based alloy, characterized in that it comprises (% by weight): lithium silicate (s) introduced in the form of an aqueous solution 3% - 35% - tensioning agent 0.01% -1% a silane, in a proportion which makes it possible to reach up to 50% by weight of the dry coating film, - water qs 100% said composition having a pH of between 11 and 13, advantageously between 11 and 12. Composition de revêtement selon la revendication 1, caractérisée en ce qu'elle comprend (% en poids): - 5 à 30% en poids, de préférence 5 à 20% en poids, plus préférentiellement 8 à 15% en poids, de silicate(s) de lithium, et/ou - environ 0,1 % en poids d'un agent de tension. Coating composition according to claim 1, characterized in that it comprises (% by weight): 5 to 30% by weight, preferably 5 to 20% by weight, more preferably 8 to 15% by weight, of lithium silicate (s), and / or about 0.1% by weight of a tensioning agent. Composition de revêtement selon l'une quelconque des revendications 1 et 2, caractérisée en ce que le silicate de lithium est utilisé dans la composition sous la forme d'une solution aqueuse de silicate de lithium de composition pondérale suivante: - - SiO2    15%-40% - - Li2O    1%-10% - - eau    qsp100% Coating composition according to either of Claims 1 and 2, characterized in that the lithium silicate is used in the composition in the form of an aqueous solution of lithium silicate of the following weight composition: - - SiO 2 15% -40% - - Li 2 O 1% -10% - - water qsp100% Composition de revêtement selon l'une quelconque des revendications 1 à 3, caractérisée en ce que l'agent de tension est choisi parmi un copolymère de polypropylèneglycol et de polyéthylènegfycol, une résine à base de silicone, un glycol acétylénique, un mélange anionique et non ionique, un ammonium quaternaire, un alcool polyéthoxylé modifié et un de leurs mélanges compatibles.Coating composition according to any one of Claims 1 to 3, characterized in that the tensioning agent is chosen from a copolymer of polypropylene glycol and of polyethylene glycol, a silicone-based resin, an acetylene glycol, an anionic and non-ionic mixture. ionic acid, a quaternary ammonium, a modified polyethoxylated alcohol and a compatible mixture thereof. Composition de revêtement selon l'une quelconque des revendications 1 à 4, caractérisée en ce qu'elle comporte en outre un polymère dont la fonction est d'abaisser la température de transition vitreuse du film sec de revêtement, en particulier un polymère ou copolymère acrylique, un polyuréthane, un alkyde, un ester d'époxy, ou un de leurs mélanges compatibles ; ledit polymère étant avantageusement ajouté à ladite composition sous la forme d'une dispersion ou d'une émulsion dans l'eau ou d'une solution aqueuse.Coating composition according to any one of claims 1 to 4, characterized in that it further comprises a polymer whose function is to lower the glass transition temperature of the dry coating film, in particular an acrylic polymer or copolymer a polyurethane, an alkyd, an epoxy ester, or a compatible mixture thereof; said polymer being advantageously added to said composition in the form of a dispersion or an emulsion in water or an aqueous solution. Composition de revêtement selon la revendication 5, caractérisée en ce que ledit polymère est ajouté à ladite composition en une proportion qui permet d'atteindre jusqu'à 60 % en poids du film sec de revêtement.Coating composition according to claim 5, characterized in that said polymer is added to said composition in a proportion which achieves up to 60% by weight of the dry coating film. Composition de revêtement selon l'une quelconque des revendications 1 à 6, caractérisée en ce qu'elle comporte en outre un additif permettant de diminuer l'alcalinité libre de surface du film sec de revêtement, en particulier un sel de cérium, un sel de lanthane, un sel de molybdène, l'acide molybdique, l'acide paratoluène sulfonique ou un polyol, ainsi que leurs mélanges, en une proportion qui permet d'atteindre jusqu'à 25% en poids du film sec de revêtement.Coating composition according to any one of claims 1 to 6, characterized in that it additionally comprises an additive which makes it possible to reduce the free surface alkalinity of the dry coating film, in particular a cerium salt, a salt of lanthanum, a molybdenum salt, molybdic acid, para-toluenesulfonic acid or a polyol, and mixtures thereof in a proportion which achieves up to 25% by weight of the dry film coating. Composition de revêtement selon l'une quelconque des revendications 1 à 7, caractérisée en ce qu'elle comporte en outre un additif permettant d'augmenter les propriétés anticorrosion du film sec de revêtement, en particulier un titanate ou un zirconate, ainsi que leurs mélanges, en une proportion qui permet d'atteindre jusqu'à 25% en poids du film sec de revêtement.Coating composition according to any one of claims 1 to 7, characterized in that it additionally comprises an additive which makes it possible to increase the anticorrosion properties of the dry coating film, in particular a titanate or a zirconate, and their mixtures in a proportion which achieves up to 25% by weight of the dry film coating. Composition de revêtement selon l'une quelconque des revendications 1 à 8, caractérisée en ce qu'elle contient en outre un agent lubrifiant, en particulier le polytétrafluoroéthylène, le polyéthylène, le polyéthylèneglycol, la cire de Carnauba, ou la paraffine, ainsi que leurs mélanges ; ledit agent de lubrifiant étant ajouté à ladite composition de revêtement en une proportion qui permet d'atteindre jusqu'à 15 % en poids du film sec de revêtement, de préférence entre 1,5 et 15% en poids du film sec de revêtement, plus préférentiellement entre 3 et 15 % en poids du film sec de revêtement, encore plus préférentiellement entre 5 et 15 % en poids du film sec de revêtement.Coating composition according to any one of claims 1 to 8, characterized in that it additionally contains a lubricating agent, in particular polytetrafluoroethylene, polyethylene, polyethylene glycol, carnauba wax, or paraffin, as well as their mixtures; said lubricant agent being added to said coating composition in a proportion which achieves up to 15% by weight of the dry film coating, preferably between 1.5 and 15% by weight of the dry film of coating, more preferably between 3 and 15% by weight of the dry film coating, more preferably between 5 and 15% by weight of the dry film coating. Composition de revêtement selon l'une quelconque des revendications 1 à 9, caractérisée en ce qu'elle comporte en outre un agent anti-mousse.Coating composition according to any one of claims 1 to 9, characterized in that it further comprises an anti-foaming agent. Composition de revêtement selon l'une quelconque des revendications 1 à 10, caractérisée par une valeur de tension superficielle comprise entre 20 mN.m-1 et 50 mN.m-1, de préférence entre 22 mN.m-1 et 45 mN.m-1, plus préférentiellement entre 22 mN.m-1 et 40 mN.m-1.Coating composition according to any one of claims 1 to 10, characterized by a surface tension value of between 20 mN.m -1 and 50 mNm -1 , preferably between 22 mNm -1 and 45 mN. m -1 , more preferably between 22 mN.m -1 and 40 mN.m -1 . Substrat métallique revêtu à l'aide d'une composition selon l'une des revendications 1 à 11.Metallic substrate coated with a composition according to one of claims 1 to 11. Procédé d'application sur substrat métallique présentant une surface extérieure libre constituée par une couche métallique à base de zinc ou d'alliage à base de zinc, d'une composition selon l'une quelconque des revendications 1 à 12, caractérisé en ce qu'il comporte une opération consistant à déposer un film humide de ladite composition, de faible épaisseur appropriée, suivie d'une opération de séchage du substrat métallique ainsi revêtu, donnant naissance à un film sec de revêtement dudit substrat.Method of application on a metal substrate having a free outer surface consisting of a metal layer based on zinc or zinc-based alloy, of a composition according to any one of Claims 1 to 12, characterized in that it comprises an operation of depositing a wet film of said composition, of suitable low thickness, followed by a drying operation of the metal substrate thus coated, giving rise to a dry coating film of said substrate. Procédé selon la revendication 13, caractérisé en ce que le film de la composition de revêtement est déposé sous la forme d'un film humide d'épaisseur comprise entre 0,3 µm et 39 µm, de préférence comprise entre 0,3 et 30 µmProcess according to Claim 13, characterized in that the film of the coating composition is deposited in the form of a wet film with a thickness of between 0.3 μm and 39 μm, preferably between 0.3 and 30 μm. Procédé selon l'une quelconque des revendications 13 et 14, caractérisé en ce que le film de la composition de revêtement est déposé sous la forme d'un film humide appliqué à raison de 0,6 g/m2 à 40 g/m2, de préférence de 0,6 à 24 g/m2.Process according to either of Claims 13 and 14, characterized in that the film of the coating composition is deposited in the form of a wet film applied at a rate of 0.6 g / m 2 to 40 g / m 2 preferably 0.6 to 24 g / m 2 . Procédé selon l'une quelconque des revendications 13 à 15, caractérisé en ce que l'opération de dépôt du film humide est effectuée : - par pulvérisation ; ou - par aspersion suivie d'une opération d'essorage du film humide déposé afin de permettre le contrôle de son épaisseur, l'opération d'essorage étant avantageusement réalisée à l'aide d'un jeu de rouleaux essoreurs ; ou - par trempage suivi d'une opération d'essorage afin de contrôler l'épaisseur du film humide déposé, l'opération d'essorage étant avantageusement réalisée à l'aide d'un jeu de rouleaux essoreurs; ou - au moyen d'un système d'enduction composé d'au moins un rouleau. A method according to any one of claims 13 to 15, characterized in that the wet film deposition operation is carried out: - by spraying; or - By sprinkling followed by a spinning operation of the wet film deposited to allow the control of its thickness, the spinning operation being advantageously carried out using a set of spinning rollers; or by dipping followed by a spinning operation in order to control the thickness of the deposited wet film, the spinning operation being advantageously carried out using a set of squeezing rolls; or by means of a coating system composed of at least one roller. Procédé selon l'une quelconque des revendications 13 à 16, caractérisé en ce que l'opération de séchage est réalisée par chauffage du substrat métallique ou du film humide de manière à porter ces derniers à une température comprise entre la température ambiante et 240°C, avantageusement l'opération de séchage est réalisée par chauffage du substrat métallique ou du film humide de manière à porter ces derniers de préférence à une température d'au moins environ 35°C pendant une durée d'au moins 2 secondes si on utilise un chauffage par convection et pendant une durée maximale de 10 secondes, de préférence de 5 secondes, plus préférentiellement de 1 à 2 secondes, si on utilise un chauffage par induction ou par infrarouge.Process according to any one of claims 13 to 16, characterized in that the drying operation is carried out by heating the metal substrate or the wet film so as to bring the latter to a temperature between room temperature and 240 ° C advantageously, the drying operation is carried out by heating the metal substrate or the wet film so as to bring the latter preferably to a temperature of at least about 35 ° C. for a period of at least 2 seconds, if using a convection heating and for a maximum of 10 seconds, preferably 5 seconds, more preferably 1 to 2 seconds, if using induction heating or infrared heating. Procédé selon l'une quelconque des revendications 13 à 17, caractérisé en ce que l'opération de séchage est conduite afin d'obtenir une épaisseur finale de film sec de revêtement comprise entre 0,05 µm et 0,080 µm, de préférence entre 0,05 et 0,60 µm.Process according to any one of Claims 13 to 17, characterized in that the drying step is carried out in order to obtain a final dry film thickness of coating of between 0.05 μm and 0.080 μm, preferably between 0 μm and 0.05 μm. 05 and 0.60 μm. Procédé selon l'une quelconque des revendications 13 à 18, caractérisé en ce que l'opération de séchage est conduite de façon à obtenir un poids de couche de film sec de revêtement compris entre 0,1 g/m2 et 1,3 g/m2, de préférence entre 0,2 g/m2 et 1,2 g/m2, plus préférentiellement entre 0,2 et 0,5 g/m2.Process according to any one of claims 13 to 18, characterized in that the drying operation is carried out so as to obtain a coating dry film thickness of between 0.1 g / m 2 and 1.3 g / m 2 , preferably between 0.2 g / m 2 and 1.2 g / m 2 , more preferably between 0.2 and 0.5 g / m 2 . Procédé selon l'une quelconque des revendications 13 à 19, caractérisé en ce que les opérations de dépôt du film humide et de séchage sont réalisées entre les opérations de revêtement métallique de zinc ou d'alliage à base de zinc dudit substrat métallique et de bobinage final.Process according to any one of Claims 13 to 19, characterized in that the wet film dewatering and drying operations are carried out between zinc metal coating operations or zinc-based alloying operations of said metal substrate and winding final. Procédé selon l'une quelconque des revendications 13 à 20, caractérisé en ce que le film sec de revêtement comprend au moins 40 % en poids de matière sèche de silicate(s) de lithium, de préférence entre 60 % et 99,9 % en poids par rapport au poids total de film sec de revêtement.Process according to any one of Claims 13 to 20, characterized in that the dry coating film comprises at least 40% by weight of lithium silicate solids, preferably between 60% and 99.9% by weight. weight relative to the total weight of dry film coating. Utilisation d'une composition de revêtement selon l'une quelconque des revendications 1 à 11 : - pour la protection anti-corrosion de tôles métalliques ; - en tant qu'agent anti-empreintes digitales, lorsqu'elle est appliquée sur des tôles métalliques ; - pour le revêtement de pièces de substrat métallique destinées à être soudées, avantageusement permettant un soudage direct desdites pièces de substrat métallique une fois revêtues de ladite composition de revêtement. Use of a coating composition according to any one of claims 1 to 11: - for anti-corrosion protection of metal sheets; - as an anti-fingerprint agent, when applied to metal sheets; for coating metal substrate parts to be welded, advantageously allowing direct welding of said metal substrate parts once coated with said coating composition. Utilisation d'une composition de revêtement selon la revendication 9 en tant que couche de lubrification lorsqu'elle est appliquée sur des tôles métalliques en vue de leur mise en forme, en particulier en vue du pliage, du cintrage et de l'emboutissage desdites tôles métalliques.Use of a coating composition according to claim 9 as a lubricating layer when applied to metal sheets for forming thereof, particularly for folding, bending and stamping said sheets metal.
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DE19814605A1 (en) * 1998-04-01 1999-10-07 Kunz Gmbh Means for sealing metallic substrates, in particular of zinc or zinc alloys

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EP1485519A2 (en) 2004-12-15
EP2208809B1 (en) 2013-06-12
EP2208809B9 (en) 2014-11-12
CA2479060A1 (en) 2003-09-25
AU2003233381A1 (en) 2003-09-29
EP1485519B1 (en) 2010-05-19
BR0308562A (en) 2005-01-04
MXPA04009082A (en) 2004-12-06
AU2003233381A8 (en) 2003-09-29
CA2479060C (en) 2011-05-24
WO2003078683A2 (en) 2003-09-25
ES2423317T3 (en) 2013-09-19
US20060086281A1 (en) 2006-04-27
ES2343244T3 (en) 2010-07-27
DE60332605D1 (en) 2010-07-01
WO2003078683A9 (en) 2004-07-15
WO2003078683A3 (en) 2004-06-03
FR2837218B1 (en) 2005-02-18
FR2837218A1 (en) 2003-09-19
ATE468424T1 (en) 2010-06-15
US7232479B2 (en) 2007-06-19

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