EP0367653A1 - Method of coating metal substrates with a powder primer and a surface coat applied by dipping, powder-primer composition and product obtained - Google Patents

Method of coating metal substrates with a powder primer and a surface coat applied by dipping, powder-primer composition and product obtained Download PDF

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Publication number
EP0367653A1
EP0367653A1 EP19890402897 EP89402897A EP0367653A1 EP 0367653 A1 EP0367653 A1 EP 0367653A1 EP 19890402897 EP19890402897 EP 19890402897 EP 89402897 A EP89402897 A EP 89402897A EP 0367653 A1 EP0367653 A1 EP 0367653A1
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EP
European Patent Office
Prior art keywords
powder
primer
coating
substrate
epoxy resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19890402897
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German (de)
French (fr)
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EP0367653B2 (en
EP0367653B1 (en
Inventor
Jean-Yves Dutheil
Eric Perraud
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Arkema France SA
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Elf Atochem SA
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/546—No clear coat specified each layer being cured, at least partially, separately
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B05D1/22—Processes for applying liquids or other fluent materials performed by dipping using fluidised-bed technique
    • B05D1/24—Applying particulate materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/58—No clear coat specified
    • B05D7/587—No clear coat specified some layers being coated "wet-on-wet", the others not
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2451/00—Type of carrier, type of coating (Multilayers)

Definitions

  • the present invention relates to a method for coating a metal substrate using a surface coating applied by dipping after coating said substrate with a powdered primer.
  • the soaking process in a fluidized bed requires a preliminary preheating of the metal part to be coated before its immersion in the tank with a porous bottom in which the powder of the coating in suspension is kept in suspension by air circulation: the powder then melts at contact with hot metal surfaces and forms a deposit, the thickness of which depends on the temperature of the substrate and its duration of immersion in the powder.
  • the part is preheated in an oven at a temperature determined according to the nature and thickness of the part to be coated.
  • an excessively high preheating temperature can be harmful, more particularly in the case where the metal part has previously been coated with an adhesion primer which can deteriorate during the passage of the part in the oven and / or no longer ensuring adhesion with the surface coating and the metal substrate.
  • the adhesion primers for surface coatings applied by dipping are exclusively in liquid form, that is to say the resins of the primer are either in suspension or in solution in one or more solvents.
  • the coating of metal substrates with these liquid primers is done for example using a pneumatic gun.
  • adhesion primers developed by the applicant are in the form of powder compositions, which can be applied as they are to metallic substrates.
  • the process for coating metallic substrates developed by the applicant implements: - a powder adhesion primer based on epoxy resin (s) and epoxy resin hardener (s), - And a surface coating applied by soaking in a fluidized bed.
  • the metal substrate which has previously been able to undergo one or more surface treatments such as alkaline degreasing, brushing, shot blasting, hot rinsing, etc., is coated with one or more layers of powder adhesion primer.
  • the metal substrate can be chosen from a wide range of products. These can be ordinary or galvanized steel parts, aluminum or aluminum alloy parts, the steel parts being more particularly targeted for the invention.
  • the thickness of the metal substrate is not critical in itself, it will most often be between 1 and 50 mm.
  • the application of the powder primer composition according to the invention can be carried out according to the powder application techniques usually used.
  • the powder application techniques there may be mentioned electrostatic spraying, a technique particularly preferred for the application of primer according to the invention, soaking in a fluidized bed.
  • the powder is introduced into a gun where it is conveyed by compressed air and passes through a nozzle brought to a high potential, generally between ten and one hundred kilovolts.
  • the applied voltage can be of positive or negative polarity, negative polarity being generally preferred.
  • the powder flow in the gun is generally between 10 and 200 g / min.
  • powders with an average particle size of between 5 and 100 ⁇ m, and preferably between 5 and 80 ⁇ m, can be used.
  • the average thickness of the primer can be between 5 and 60 ⁇ m, and preferably between 10 and 20 ⁇ m.
  • the powder compositions which constitute the adhesion primer according to the invention are based on solid thermosetting resins and preferably based on epoxy resins and epoxy resin hardener (s).
  • thermosetting resin is meant in the present description epoxy resins, phenolic resins, epoxyphenolic precondensates, alone or as a mixture.
  • epoxy resins By way of example of advantageously preferred epoxy resins, mention may be made of the products obtained by reaction of bisphenol-A and of epichlorohydrin and the degree of polymerization of which is greater than two, as well as the high molecular weight polycondensates of phenoxy type without free reactive group.
  • phenolic resins examples include the resins obtained by polycondensation of formaldehyde and of a phenol.
  • amine-type compound means aliphatic or aromatic amines and their derivatives, such as dicyandiamide, benzyldimethylamine, boron trifluoride monoethylamine.
  • acid anhydride By way of example of acid anhydride, mention may be made of aromatic anhydrides such as phthalic anhydride or cycloaliphtalic anhydrides such as hexahydrophthalic anhydride.
  • isocyanate type compound means a monomer, prepolymer or polymer compound containing at least two free or blocked isocyanate groups.
  • Polyisocyanate compounds with an aromatic or aliphatic structure whose isocyanate groups are blocked by condensation with phenol or caprolactam are particularly preferred.
  • the proportion of epoxy resin (s) and hardener (s) of the amine, acid anhydride or isocyanate type must be such that the number of epoxy functions is equal to the number of reactive functions of the amine of the acid anhydride or of the isocyanate compound.
  • the primers in accordance with the invention may also contain various additives and agents, alone or as a mixture, such as pigments, fillers, corrosion inhibiting agents, etc.
  • additives and agents such as pigments, fillers, corrosion inhibiting agents, etc.
  • strontium chromate such as strontium chromate.
  • zinc phosphate titanium dioxide
  • silica such as silica
  • the substrate is placed in an oven where it is heated to a determined temperature depending in particular on the nature of said substrate, its shape and the desired coating thickness.
  • the energy stored during the passage through the oven of the substrate coated with primer allows, in addition to the crosslinking of the primer, the melting and the adhesion of the surface coating applied by dipping on the substrate as soon as it leaves the oven.
  • the powder adhesion primers developed by the applicant resist particularly well at the high temperatures which may be necessary to ensure effective preheating of the substrate to be coated.
  • the powder primers according to the invention can not only be heated to 270-320 ° C, but they can, without damage to the quality of the final coating, undergo heating at higher temperatures, such as for example between 320 and 380 ° C, when necessary.
  • the average residence time of the substrate in the oven is generally between 1 and 30 min and preferably between 3 and 10 min.
  • the substrate is immersed in a soaking tank containing the surface coating as defined above.
  • the surface coatings in powder form, applied by dipping and in accordance with the invention are preferably based on polyamide and / or polyetheresteramide.
  • polyamide entering the powder surface coating is meant the aliphatic polyamides obtained from lactams or amino acids whose hydrocarbon chain has a number of carbon atoms between 4 and 20 such as, for example, caprolactam, enantholactam, dodecalactam, undecanolactam, 11-undecanoic amino acid, 12-dodecanoic amino acid, the condensation products of a dicarboxylic acid with a diamine such as, for example, polyamides 6.6 , 6.10, 6.12, 9.6, (products of the condensation of hexamethylene diamine with adipic acid, azelaic acid, sebacic acid, dodecanedioic acid-1,12 and nonamethylene diamine with acid adipic), the copolyamides resulting from the polymerization of the various monomers mentioned above or the mixtures of several polyamides mentioned above.
  • polyamide 11 obtained by polycondensation of amino-11 undecanoic acid
  • polyamide 12 obtained by polycondensation of 12-amino-dodecanoic acid or of dodecanolactam
  • copolyamides obtained by the polymerization of the monomers mentioned above.
  • the inherent viscosity (measured at 20 ° C for a solution of 0.5 g per 100 g of metacresol) of the polyamides can be between 0.20 and 2.0, and preferably between 0.60 and 1.30 dlg ⁇ 1.
  • polyamides also means semi-aromatic amorphous polyamides, and in particular as defined in French patents FR 1,588,130, 2,324,672 and 2,575,756, in European patent EP 53,876, in Japanese patents 59,015,447 and 60,217,237.
  • polyetheresteramides is intended to mean both the random polyetheresteramides (that is to say formed by the random sequence of the various monomer components) and the block polyetheresteramides, that is to say formed from blocks having a certain length of chain. their various constituents.
  • Polyetheresteramides are products of the copolycondensation of polyamide blocks with reactive ends with polyether sequences with reactive ends such as: - polyamide sequences for dicarboxylic chain ends with polyetherdiol sequences.
  • the number-average molecular mass of these polyamide blocks is generally between 500 and 10,000 and more particularly between 600 and 5,000.
  • the polyamide blocks of the polyetheresteramides are preferably formed from polyamide 6, 6.6, 6.12, 11 or 12 or from copolyamides resulting from the polycondensation of their monomers.
  • the number average molecular weight of the polyethers is generally between 200 and 6000 and more particularly between 600 and 3000.
  • the polyether blocks preferably consist of polytetramethylene glycol (PTMG), polypropylene glycol (PPG), or polyethylene glycol (PEG).
  • PTMG polytetramethylene glycol
  • PPG polypropylene glycol
  • PEG polyethylene glycol
  • the inherent viscosity of polyetheresteramides is advantageously between 0.8 and 2.05, and preferably between 0.80 and 1.20.
  • the inherent viscosity is measured in metacresol at 25 ° C with an initial concentration of 0.5 g per 100 g of metacresol. It is expressed in dlg ⁇ 1.
  • the polyetheresteramides according to the invention can be formed from 5 to 85% by weight of polyether and from 95 to 15% by weight of polyamide, and preferably from 30 to 80% by weight of polyether and from 70 to 20% by weight of polyamide.
  • the particle size of the surface coating powders can be between 20 and 300 ⁇ m, and preferably between 40 and 200 ⁇ m.
  • the soaking technique according to the invention is carried out in a non-electrostatic fluidized bed, the electrostatic fluidized beds being unsuitable and difficult to use for soaking in powders based on polyamide and / or polyetheresteramide which are particularly preferred by the applicant. .
  • the thickness of the surface coating can be between 150 and 600 ⁇ m, and preferably between 200 and 400 ⁇ m.
  • the substrate is cooled, for example with ambient air, by immersion in water or in any other suitable solvent, after having possibly undergone a post-melting.
  • the metal substrate consists of a steel plate 1 mm thick. This plate has previously been degreased and then shot blasted. 2 °)
  • the particle size of the primer composition is less than 80 ⁇ m. 3)
  • the surface coating consists of PA-11, in the form of a powder with a particle size between 40 and 200 ⁇ m. The inherent viscosity of PA-11, measured at 20 ° C for a solution of 0.5 g of polymer in 100 g of m-cresol, is equal to 1.
  • the powdered primer composition as described in A. 2 °) is deposited at room temperature on the steel plate by electrostatic spraying under a negative electrostatic charge of 40 kV, the metal surface being at potential O.
  • the substrate thus coated passes through an oven maintained at 380 ° C where it remains for 3 min.
  • the substrate thus coated is removed from the soaking tank and then cooled in air after post-melting.
  • the metal substrate is a sandblasted steel plate and the surface coating has the same characteristics as those of EXAMPLE 1.
  • the substrate is coated with the primer by electrostatic spraying under the same conditions as in 1.B.
  • the material obtained is a composite comprising successively: - a sandblasted steel plate (thickness 3 mm) - a primer layer of average thickness equal to 20 ⁇ m - a surface coating layer of thickness between 200 and 250 ⁇ m.
  • the materials undergo an adhesion test carried out according to standard NF T 58-112 and a salt spray aging test carried out according to standard NF X 41-002.
  • EXAMPLE 1 The test of EXAMPLE 1 is repeated using a powdered primer which comprises (in g).
  • A) - modified novolak epoxy resin (epoxy equivalent weight: 500-575; softening point between 90 and 98 ° C; d 1.19) 92 - micronized dicyandiamide 8
  • B) - poly p. vinylphenol Mw between 2000 and 30000, of epoxy equivalent weight 120 and having a softening weight between 140 and 210 ° C. 100
  • the metal substrate and the surface coating have the same characteristics as in EXAMPLE 2 and the conditions for placing work and evaluation of the materials obtained are identical to those described in EXAMPLE 2.
  • liquid primer which comprises the following resins: - epoxy resin obtained by reaction of epichlorohydrin and bisphenol A whose molecular mass is between 3000 and 3800 g and the weight of epoxide equivalent between 1600 and 4000. - resol phenophenol type resin - aminoplast melamine-formaldehyde resin dissolved in a mixture of ethylene glycol, solvent naphtha, butanol, isobutanol and methyl isobutyl ketone.
  • the metal substrate and the surface coating have the same characteristics as those of EXAMPLE 1.
  • the material obtained is such that the initial adhesion of the coating is zero (Class O) and the corrosion path is complete in a few hours.
  • a two-layer coating comprising - an epoxy undercoat (42% of the total thickness of the coating) - a polyamide layer, the total thickness of the coating being equal to 260 ⁇ m.

Abstract

The present invention relates to the field of coatings of metal substrates applied by dipping. It relates to a method of coating a metal substrate using a surface coat applied by dipping after coating of said substrate with a powder primer. It also relates to powder compositions which can be used as adhesion primer, as well as to composite materials: metal substrates/adhesion primer/surface coat.

Description

La présente invention concerne un procédé pour revêtir un substrat métallique à l'aide d'un revêtement superficiel appliqué par trempage après enduction dudit substrat avec un primaire en poudre.The present invention relates to a method for coating a metal substrate using a surface coating applied by dipping after coating said substrate with a powdered primer.

Le procédé de trempage en lit fluidisé nécessite un préchauffage préalable de la pièce métallique à revêtir avant son immersion dans la cuve à fond poreux dans laquelle la poudre du revêtement en suspension est maintenue en suspension par une circulation d'air : la poudre fond alors au contact des surfaces métalliques chaudes et forme un dépôt dont l'épaisseur est fonction de la température du substrat et de sa durée d'immersion dans la poudre.The soaking process in a fluidized bed requires a preliminary preheating of the metal part to be coated before its immersion in the tank with a porous bottom in which the powder of the coating in suspension is kept in suspension by air circulation: the powder then melts at contact with hot metal surfaces and forms a deposit, the thickness of which depends on the temperature of the substrate and its duration of immersion in the powder.

Le préchauffage de la pièce s'effectue dans un four à une température déterminée suivant la nature et l'épaisseur de la pièce à revêtir.The part is preheated in an oven at a temperature determined according to the nature and thickness of the part to be coated.

Mais pour une pièce donnée, il existe une température minimale au-dessous de laquelle il n'est pas possible d'obtenir un revêtement de bonne qualité du point de vue de son aspect et de son adhérence au substrat.However, for a given part, there is a minimum temperature below which it is not possible to obtain a coating of good quality from the point of view of its appearance and of its adhesion to the substrate.

Mais, d'autre part, une température de préchauffage trop élevée peut être nuisible, plus particulièrement dans le cas où on a préala­blement revêtu la pièce métallique d'un primaire d'adhérence qui peut se dégrader lors du passage de la pièce dans le four et/ou ne plus assurer d'adhérence avec le revêtement superficiel et le substrat métallique.But, on the other hand, an excessively high preheating temperature can be harmful, more particularly in the case where the metal part has previously been coated with an adhesion primer which can deteriorate during the passage of the part in the oven and / or no longer ensuring adhesion with the surface coating and the metal substrate.

A l'heure actuelle, les primaires d'adhérence pour revêtements superficiels appliqués par trempage se présentent exclusivement sous forme liquide, c'est-à-dire les résines du primaire se trouvent soit en suspension, soit en solution dans un ou plusieurs solvants. L'enduction des substrats métalliques avec ces primaires liquides se fait par exemple à l'aide d'un pistolet pneumatique.At present, the adhesion primers for surface coatings applied by dipping are exclusively in liquid form, that is to say the resins of the primer are either in suspension or in solution in one or more solvents. The coating of metal substrates with these liquid primers is done for example using a pneumatic gun.

Ces solvants, souvent toxiques pour l'environnement, obligent à prévoir des systèmes de récupération et/ou de recyclage, entraînant ainsi un surcoût de l'installation.These solvents, often toxic to the environment, require the provision of recovery and / or recycling systems, thus resulting in additional cost to the installation.

Les primaires d'adhérence mis au point par la demanderesse se présentent sous forme de compositions en poudre, applicables telles quelles sur les substrats métalliques.The adhesion primers developed by the applicant are in the form of powder compositions, which can be applied as they are to metallic substrates.

Le procédé de revêtement de substrats métalliques mis au point par la demanderesse met en oeuvre :
- un primaire d'adhérence en poudre à base de résine(s) époxyde(s) et de durcisseurs de résine(s) époxyde(s),
- et un revêtement superficiel appliqué par trempage en lit fluidisé.The process for coating metallic substrates developed by the applicant implements:
- a powder adhesion primer based on epoxy resin (s) and epoxy resin hardener (s),
- And a surface coating applied by soaking in a fluidized bed.

Le procédé mis au point par la demanderesse est caractérisé en ce qu'il comprend les étapes suivantes :

  • a) enduction du substrat avec une ou plusieurs couches de primaire d'adhérence selon une technique d'application en poudre,
  • b) chauffage du substrat et immédiatement après :
  • c) application par trempage en lit fluidisé du revêtement superficiel en poudre.
The process developed by the applicant is characterized in that it comprises the following stages:
  • a) coating the substrate with one or more layers of adhesion primer according to a powder application technique,
  • b) heating of the substrate and immediately after:
  • c) application by soaking in a fluidized bed of the surface powder coating.

Le substrat métallique qui a préalablement pu subir un ou plusieurs traitements de surface tels que dégraissage alcalin, brossage, grenaillage phosphatation, rinçage à chaud..., est revêtu d'une ou plusieurs couches de primaire d'adhérence en poudre.The metal substrate which has previously been able to undergo one or more surface treatments such as alkaline degreasing, brushing, shot blasting, hot rinsing, etc., is coated with one or more layers of powder adhesion primer.

Le substrat métallique peut être choisi dans une large gamme de produits. Il peut s'agir de pièces d'acier ordinaire ou galvanisé, de pièces en aluminium ou en alliage d'aluminium, les pièces en acier étant plus particulièrement visées pour l'invention.The metal substrate can be chosen from a wide range of products. These can be ordinary or galvanized steel parts, aluminum or aluminum alloy parts, the steel parts being more particularly targeted for the invention.

Bien que l'épaisseur du substrat métallique ne soit pas critique en elle-même, elle se situera le plus souvent entre 1 et 50 mm.Although the thickness of the metal substrate is not critical in itself, it will most often be between 1 and 50 mm.

L'application de la composition de primaire en poudre selon l'invention peut s'effectuer selon les techniques d'application de poudre habituellement mises en oeuvre. Parmi les techniques d'appli­cation de poudre, on peut citer la projection électrostatique, technique particulièrement préférée pour l'application de primaire selon l'invention, le trempage en lit fluidisé.The application of the powder primer composition according to the invention can be carried out according to the powder application techniques usually used. Among the powder application techniques, there may be mentioned electrostatic spraying, a technique particularly preferred for the application of primer according to the invention, soaking in a fluidized bed.

En projection électrostatique la poudre est introduite dans un pistolet où elle est véhiculée par de l'air comprimé et passe dans une buse portée à un potentiel élevé, en général compris entre une dizaine et une centaine de kilovolts.In electrostatic projection the powder is introduced into a gun where it is conveyed by compressed air and passes through a nozzle brought to a high potential, generally between ten and one hundred kilovolts.

La tension appliquée peut être de polarité positive ou négative, la polarité négative étant en général préférée.The applied voltage can be of positive or negative polarity, negative polarity being generally preferred.

Le débit de la poudre dans le pistolet est généralement compris entre 10 et 200 g/mn.The powder flow in the gun is generally between 10 and 200 g / min.

En général, on peut utiliser des poudres de granulométrie moyenne comprise entre 5 et 100 µm, et de préférence entre 5 et 80 µm.In general, powders with an average particle size of between 5 and 100 μm, and preferably between 5 and 80 μm, can be used.

L'épaisseur moyenne du primaire peut être comprise entre 5 et 60 µm, et de préférence entre 10 et 20 µm.The average thickness of the primer can be between 5 and 60 µm, and preferably between 10 and 20 µm.

Les compositions en poudre qui constituent le primaire d'adhérence conforme à l'invention sont à base de résines thermodurcissables solides et de préférence à base de résines époxydes et de durcisseur(s) de résine(s) époxyde(s).The powder compositions which constitute the adhesion primer according to the invention are based on solid thermosetting resins and preferably based on epoxy resins and epoxy resin hardener (s).

Par résine thermodurcissable, on entend dans la présente descrip­tion les résines époxydes, les résines phénoliques, les précondensats époxyphénoliques, seuls ou en mélange.By thermosetting resin is meant in the present description epoxy resins, phenolic resins, epoxyphenolic precondensates, alone or as a mixture.

A titre d'exemple de résines époxydes avantageusement préférées, on peut citer les produits obtenus par réaction du bisphénol-A et de l'épichlorhydrine et dont le degré de polymérisation est supérieur à deux ainsi que les polycondensats de haut poids moléculaire de type phénoxy sans groupement réactif libre.By way of example of advantageously preferred epoxy resins, mention may be made of the products obtained by reaction of bisphenol-A and of epichlorohydrin and the degree of polymerization of which is greater than two, as well as the high molecular weight polycondensates of phenoxy type without free reactive group.

A titre d'exemple de résines phénoliques avantageusement préfé­rées, on peut citer les résines obtenues par polycondensation du formaldéhyde et d'un phénol.As examples of advantageously preferred phenolic resins, mention may be made of the resins obtained by polycondensation of formaldehyde and of a phenol.

Parmi les différents durcisseurs solides de résine(s) époxyde(s), on utilise de préférence les composés de type amine, anhydride d'acide ou isocyanate.Among the various solid hardeners of epoxy resin (s), compounds of the amine, acid anhydride or isocyanate type are preferably used.

Par composé de type amine, on entend les amines aliphatiques ou aromatiques et leurs dérivés, tels que la dicyandiamide, la benzyldi­méthylamine, le trifluorure de bore monoéthylamine.The term “amine-type compound” means aliphatic or aromatic amines and their derivatives, such as dicyandiamide, benzyldimethylamine, boron trifluoride monoethylamine.

A titre d'exemple d'anhydride d'acide, on peut citer les anhy­drides, aromatiques tels que l'anhydride phtalique ou cycloaliphta­liques tels que l'anhydride hexahydrophtalique.By way of example of acid anhydride, mention may be made of aromatic anhydrides such as phthalic anhydride or cycloaliphtalic anhydrides such as hexahydrophthalic anhydride.

Par composé de type isocyanate, on entend un composé monomère, prépolymère ou polymère contenant au moins deux groupements isocyanates libres ou bloqués. Les composés polyisocyanates à structure aromatique ou aliphatique dont les groupements isocyanates sont bloqués par condensation avec le phénol ou le caprolactame sont particulièrement préférés.The term “isocyanate type compound” means a monomer, prepolymer or polymer compound containing at least two free or blocked isocyanate groups. Polyisocyanate compounds with an aromatic or aliphatic structure whose isocyanate groups are blocked by condensation with phenol or caprolactam are particularly preferred.

La proportion de résine(s) époxyde(s) et de durcisseur(s) de type amine, anhydride d'acide ou isocyanate doit être telle que le nombre de fonctions époxydes soit égal au nombre de fonctions réactives de l'amine de l'anhydride d'acide ou du composé isocyanate.The proportion of epoxy resin (s) and hardener (s) of the amine, acid anhydride or isocyanate type must be such that the number of epoxy functions is equal to the number of reactive functions of the amine of the acid anhydride or of the isocyanate compound.

Cependant, pour des raisons de qualité du revêtement, on peut préférer faire varier la proportion stoechiométrique indiquée ci-dessus entre 0,1 et 1,5 fonctions réactives amines anhydrides ou isocyanates pour une fonction époxyde.However, for reasons of coating quality, it may be preferable to vary the stoichiometric proportion indicated above between 0.1 and 1.5 reactive anhydride or isocyanate amine functions for an epoxide function.

Les primaires conformes à l'invention peuvent également contenir des additifs et agents divers, seuls ou en mélange, tels que des pigments, des charges, des agents inhibiteurs de corrosion... Parmi les composés habituellement rencontrés, on peut citer le chromate de strontium, le phosphate de zinc, le dioxyde de titane, la silice.The primers in accordance with the invention may also contain various additives and agents, alone or as a mixture, such as pigments, fillers, corrosion inhibiting agents, etc. Among the compounds usually encountered, mention may be made of strontium chromate. , zinc phosphate, titanium dioxide, silica.

Une fois l'application du primaire sur le substrat terminée, on place le substrat dans un four où il est chauffé à une température déterminée suivant notamment la nature dudit substrat, sa forme et l'épaisseur de revêtement désirée. L'énergie stockée lors du passage dans le four du substrat revêtu de primaire permet, outre la réticu­lation du primaire, la fusion et l'adhérence du revêtement superficiel appliqué par trempage sur le substrat dès sa sortie du four.Once the primer has been applied to the substrate, the substrate is placed in an oven where it is heated to a determined temperature depending in particular on the nature of said substrate, its shape and the desired coating thickness. The energy stored during the passage through the oven of the substrate coated with primer allows, in addition to the crosslinking of the primer, the melting and the adhesion of the surface coating applied by dipping on the substrate as soon as it leaves the oven.

Les primaires d'adhérence en poudre mis au point par la demande­resse résistent particulièrement bien aux températures élevées qui peuvent être nécessaires pour assurer un préchauffage efficace du substrat à revêtir.The powder adhesion primers developed by the applicant resist particularly well at the high temperatures which may be necessary to ensure effective preheating of the substrate to be coated.

Tel n'est pas le cas des primaires liquides pour lesquels une température trop élevée nuit aux résultats d'adhérence du revêtement final ; c'est pourquoi les conditions normales d'utilisation des primaires liquides sont limitées aux revêtements de pièces métalliques de configuration géométrique telle que la température du préchauffage avant trempage qui est nécessaire est inférieure à 270-320°C.This is not the case for liquid primers for which too high a temperature adversely affects the adhesion results of the final coating; this is why the normal conditions of use of liquid primers are limited to coatings of metal parts of geometric configuration such that the temperature of preheating before soaking which is necessary is less than 270-320 ° C.

Les primaires en poudre selon l'invention peuvent non seulement être chauffés à 270-320°C, mais ils peuvent, sans dommage pour la qualité du revêtement final, subir un chauffage à des températures plus élevées, telles que par exemple, entre 320 et 380°C, lorsque c'est nécessaire.The powder primers according to the invention can not only be heated to 270-320 ° C, but they can, without damage to the quality of the final coating, undergo heating at higher temperatures, such as for example between 320 and 380 ° C, when necessary.

Le temps de séjour moyen du substrat dans le four est en général compris entre 1 et 30 mn et de préférence entre 3 et 10 mn.The average residence time of the substrate in the oven is generally between 1 and 30 min and preferably between 3 and 10 min.

Dès sa sortie du four, le substrat est plongé dans une cuve de trempage contenant le revêtement superficiel tel que défini précédem­ment.As soon as it leaves the oven, the substrate is immersed in a soaking tank containing the surface coating as defined above.

Les revêtements superficiels en poudre, appliqués par trempage et conformes à l'invention sont de préférence à base de polyamide et/ou de polyétheresteramide.The surface coatings in powder form, applied by dipping and in accordance with the invention are preferably based on polyamide and / or polyetheresteramide.

Par polyamide entrant dans le revêtement superficiel en poudre selon l'invention, on entend les polyamides aliphatiques obtenus à partir de lactames ou d'aminoacides dont la chaîne hydrocarbonée possède un nombre d'atomes de carbone compris entre 4 et 20 comme, par exemple, le caprolactame, l'oénantholactame, le dodécalactame, l'undé­canolactame, l'acide amino 11-undécanoïque, l'acide amino 12-dodéca­noïque, les produits de condensation d'un acide dicarboxylique avec une diamine comme, par exemple, les polyamides 6.6, 6.10, 6.12, 9.6, (produits de la condensation de l'hexaméthylène diamine avec l'acide adipique, l'acide azélaïque, l'acide sébacique, l'acide dodécane­dioïque-1,12 et de la nonaméthylène diamine avec l'acide adipique), les copolyamides résultant de la polymérisation des divers monomères cités ci-dessus ou les mélanges de plusieurs polyamides cités ci-dessus.By polyamide entering the powder surface coating according to the invention, is meant the aliphatic polyamides obtained from lactams or amino acids whose hydrocarbon chain has a number of carbon atoms between 4 and 20 such as, for example, caprolactam, enantholactam, dodecalactam, undecanolactam, 11-undecanoic amino acid, 12-dodecanoic amino acid, the condensation products of a dicarboxylic acid with a diamine such as, for example, polyamides 6.6 , 6.10, 6.12, 9.6, (products of the condensation of hexamethylene diamine with adipic acid, azelaic acid, sebacic acid, dodecanedioic acid-1,12 and nonamethylene diamine with acid adipic), the copolyamides resulting from the polymerization of the various monomers mentioned above or the mixtures of several polyamides mentioned above.

Parmi ces polyamides on citera tout particulièrement :
- le polyamide 11, obtenu par polycondensation de l'acide amino-11 undécanoïque,
- le polyamide 12, obtenu par polycondensation de l'acide amino-12 dodécanoïque ou du dodécanolactame et,
- les copolyamides obtenus par la polymérisation des monomères cités ci-dessus.Among these polyamides, special mention will be made of:
polyamide 11, obtained by polycondensation of amino-11 undecanoic acid,
polyamide 12, obtained by polycondensation of 12-amino-dodecanoic acid or of dodecanolactam and,
- the copolyamides obtained by the polymerization of the monomers mentioned above.

D'une manière générale, la viscosité inhérente (mesurée à 20°C pour une solution à 0,5 g pour 100 g de métacrésol) des polyamides peut être comprise entre 0,20 et 2,0, et de préférence entre 0,60 et 1,30 dlg⁻¹.In general, the inherent viscosity (measured at 20 ° C for a solution of 0.5 g per 100 g of metacresol) of the polyamides can be between 0.20 and 2.0, and preferably between 0.60 and 1.30 dlg⁻¹.

Par polyamides, on entend aussi les polyamides amorphes semi-aromatiques, et notamment tels que définis dans les brevets français FR 1 588 130, 2 324 672 et 2 575 756, dans le brevet européen EP 53 876, dans les brevets Japonais 59 015 447 et 60 217 237.The term “polyamides” also means semi-aromatic amorphous polyamides, and in particular as defined in French patents FR 1,588,130, 2,324,672 and 2,575,756, in European patent EP 53,876, in Japanese patents 59,015,447 and 60,217,237.

Par polyétheresteramides, on entend aussi bien les polyéther­esteramides statistiques (c'est-à-dire formés par l'enchaînement aléatoire des divers constituants monomères) que les polyétherester­amides séquencés c'est-à-dire formés de blocs présentant une certaine longueur de chaîne de leurs divers constituants.The term “polyetheresteramides” is intended to mean both the random polyetheresteramides (that is to say formed by the random sequence of the various monomer components) and the block polyetheresteramides, that is to say formed from blocks having a certain length of chain. their various constituents.

Les polyétheresteramides sont des produits de la copolyconden­sation de séquences polyamides à extrémités réactives avec des séquences polyéthers à extrémités réactives telles que :
- séquences polyamides à fins de chaîne dicarboxyliques avec des séquences polyétherdiols.Polyetheresteramides are products of the copolycondensation of polyamide blocks with reactive ends with polyether sequences with reactive ends such as:
- polyamide sequences for dicarboxylic chain ends with polyetherdiol sequences.

La masse moléculaire moyenne en nombre de ces séquences polyamides est généralement comprise entre 500 et 10 000 et plus particulièrement entre 600 et 5 000. Les séquences polyamides des polyétheresteramides sont formées de préférence de polyamide 6, 6.6, 6.12, 11 ou 12 ou de copolyamides résultant de la polycondensation de leurs monomères.The number-average molecular mass of these polyamide blocks is generally between 500 and 10,000 and more particularly between 600 and 5,000. The polyamide blocks of the polyetheresteramides are preferably formed from polyamide 6, 6.6, 6.12, 11 or 12 or from copolyamides resulting from the polycondensation of their monomers.

La masse moléculaire moyenne en nombre des polyéthers est comprise généralement entre 200 et 6 000 et plus particulièrement entre 600 et 3 000.The number average molecular weight of the polyethers is generally between 200 and 6000 and more particularly between 600 and 3000.

Les séquences polyéthers consistent de préférence en polytétramé­thylène glycol (PTMG), polypropylène glycol (PPG), ou polyéthylène glycol (PEG).The polyether blocks preferably consist of polytetramethylene glycol (PTMG), polypropylene glycol (PPG), or polyethylene glycol (PEG).

La viscosité inhérente des polyétheresteramides est avantageu­sement comprise entre 0,8 et 2,05, et de préférence entre 0,80 et 1,20.The inherent viscosity of polyetheresteramides is advantageously between 0.8 and 2.05, and preferably between 0.80 and 1.20.

La viscosité inhérente est mesurée dans le métacrésol à 25°C avec une concentration initiale de 0,5 g pour 100 g de métacrésol. Elle est exprimée en dlg⁻¹.The inherent viscosity is measured in metacresol at 25 ° C with an initial concentration of 0.5 g per 100 g of metacresol. It is expressed in dlg⁻¹.

Les polyétheresteramides selon l'invention peuvent être formés de 5 à 85 % en poids de polyéther et de 95 à 15 % en poids de polyamide, et de préférence de 30 à 80 % en poids de polyéther et de 70 à 20 % en poids de polyamide.The polyetheresteramides according to the invention can be formed from 5 to 85% by weight of polyether and from 95 to 15% by weight of polyamide, and preferably from 30 to 80% by weight of polyether and from 70 to 20% by weight of polyamide.

La granulométrie des poudres de revêtement superficiel peut être comprise entre 20 et 300 µm, et de préférence entre 40 et 200 µm.The particle size of the surface coating powders can be between 20 and 300 μm, and preferably between 40 and 200 μm.

La technique de trempage selon l'invention est menée dans un lit fluidisé non électrostatique, les lits fluidisés électrostatiques étant peu adaptés et de mise en oeuvre difficile pour le trempage dans des poudres à base de polyamide et/ou de polyétheresteramide particuliè­rement préférées par la demanderesse.The soaking technique according to the invention is carried out in a non-electrostatic fluidized bed, the electrostatic fluidized beds being unsuitable and difficult to use for soaking in powders based on polyamide and / or polyetheresteramide which are particularly preferred by the applicant. .

En général, l'épaisseur du revêtement superficiel peut être comprise entre 150 et 600 µm, et de préférence entre 200 et 400 µm.In general, the thickness of the surface coating can be between 150 and 600 μm, and preferably between 200 and 400 μm.

Une fois l'opération de trempage terminée, le substrat est refroidi, par exemple à l'air ambiant, par immersion dans l'eau ou dans tout autre solvant approprié, après avoir éventuellement subi une post-fusion.Once the soaking operation has ended, the substrate is cooled, for example with ambient air, by immersion in water or in any other suitable solvent, after having possibly undergone a post-melting.

Les exemples suivant illustrent l'invention sans toutefois la limiter.The following examples illustrate the invention without, however, limiting it.

EXEMPLE 1EXAMPLE 1 A) CONSTITUANTSA) CONSTITUENTS


1°) Le substrat métallique est constitué par une plaque d'acier de 1 mm d'épaisseur. Cette plaque a préalablement subi un dégraissage puis un grenaillage.
2°) La composition de primaire en poudre comprend (en grammes) : - résine époxyde obtenue par réaction de l'épichlorhydrine et du bisphénol A. (masse moléculaire : 1400 g ; poids d'équivalent époxyde : 850-950 ; point de ramollissement : 90°C) 90 - composé d'isocyanate (polyisocyanate aromatique bloqué à teneur en -N=C=O égale à 14 % ; densité : 1,27) 10 La granulométrie de la composition de primaire est inférieure à 80 µm.
3°) Le revêtement superficiel est constitué par du PA-11, sous forme de poudre de granulométrie comprise entre 40 et 200 µm.

La viscosité inhérente du PA-11, mesurée à 20°C pour une solution de 0,5 g de polymère dans 100 g de m-crésol, est égale à 1.
1 °) The metal substrate consists of a steel plate 1 mm thick. This plate has previously been degreased and then shot blasted.
2 °) The composition of powdered primer includes (in grams): - epoxy resin obtained by reaction of epichlorohydrin and bisphenol A. (molecular mass: 1400 g; weight of epoxide equivalent: 850-950; softening point: 90 ° C) 90 - isocyanate compound (blocked aromatic polyisocyanate with -N = C = O content equal to 14%; density: 1.27) 10 The particle size of the primer composition is less than 80 μm.
3) The surface coating consists of PA-11, in the form of a powder with a particle size between 40 and 200 μm.

The inherent viscosity of PA-11, measured at 20 ° C for a solution of 0.5 g of polymer in 100 g of m-cresol, is equal to 1.

B) MISE EN OEUVREB) IMPLEMENTATION

La composition de primaire en poudre telle que décrite en A. 2°) est déposée à température ambiante sur la plaque d'acier par projection électrostatique sous charge électrostatique négative de 40 kV, la surface métallique étant à potentiel O.The powdered primer composition as described in A. 2 °) is deposited at room temperature on the steel plate by electrostatic spraying under a negative electrostatic charge of 40 kV, the metal surface being at potential O.

Le substrat ainsi revêtu passe dans un four maintenu à 380°C où il séjourne pendant 3 mn.The substrate thus coated passes through an oven maintained at 380 ° C where it remains for 3 min.

Immédiatement après, il est immergé dans une cuve de trempage en lit fluidisé contenant de la poudre de PA-11 tel que définie en A.3°).Immediately afterwards, it is immersed in a soaking tank in a fluidized bed containing PA-11 powder as defined in A.3 °).

Après environ 4 secondes d'immersion, le substrat ainsi revêtu est retiré de la cuve de trempage puis refroidi à l'air après post-fusion.After approximately 4 seconds of immersion, the substrate thus coated is removed from the soaking tank and then cooled in air after post-melting.

C) CARACTERISTIQUES DU MATERIAUC) CHARACTERISTICS OF THE MATERIAL

  • 1°) Le matériau est un composite comprenant successivement :
    - une plaque d'acier sablée (épaisseur 1 mm)
    - une couche de primaire d'épaisseur moyenne égale à 20 µm.
    - une couche de revêtement superficiel d'épaisseur comprise entre 200 et 250 µm.    1 °) The material is a composite comprising successively:
    - a sandblasted steel plate (thickness 1 mm)
    - a primer layer of average thickness equal to 20 µm.
    - a surface coating layer of thickness between 200 and 250 µm.
  • 2°) Le matériau décrit en C.1°) subit un test d'adhérence réalisé selon la norme NF T 58-112.2 °) The material described in C.1 °) undergoes an adhesion test carried out according to standard NF T 58-112.

On obtient le résultat d'adhérence suivant :
Classe 4 (très bonne adhérence).The following adhesion result is obtained:
Class 4 (very good adhesion).

Le matériau décrit ci-dessus subit un test de vieillissement au brouillard salin réalisé selon la norme NF X 41-002.The material described above undergoes a salt spray aging test carried out according to standard NF X 41-002.

Après 2000 heures d'essai, on obtient les résultats suivants :
- adhérence mesurée selon la norme NF T 58-112 :
Classe 3,5-4 (très bonne adhérence).
- cheminement à partir d'une entaille en croix : 11 mm.
- cloquage mesuré selon la norme ASTM D 56(81) :
Classe 10 (pas de cloquage).After 2000 hours of testing, the following results are obtained:
- adhesion measured according to standard NF T 58-112:
Class 3.5-4 (very good adhesion).
- routing from a cross notch: 11 mm.
- blistering measured according to ASTM D 56 (81):
Class 10 (no blistering).

EXEMPLE 2EXAMPLE 2

On renouvelle l'essai de l'EXEMPLE 1 en utilisant différents primaires en poudre dont la composition comprend (en grammes) : EXEMPLE 2.A - résine époxyde obtenue par réaction de l'épichlorhydrine et du bisphénol A. (masse moléculaire : 1400 g ; poids d'équivalent époxyde : 850-950 ; point de ramollissement : 90°C) 90 - résine dicyandiamide catalysée ou micronisée 10 EXEMPLE 2.B - résine époxyde de mêmes caractéristiques qu'en 2.A 92,5 - anhydride phtalique 7,5 EXEMPLE 2.C - résine époxyde de mêmes caractéristiques qu'en 2.A 92 - diamino diphénylsulfone 8 EXEMPLE 2.D - résine époxyde de mêmes caractéristiques qu'en 2.A 50 - résine polyester saturée (indice d'acide : 70-85 ; Tg = 55°C) 50 EXEMPLE 2.E - résine époxyde de mêmes caractéristiques qu'en 2.A 50 - résine phénol/aldéhyde (point de fusion : 100°C ; aldéhyde/phénol : 1,2 (en M) ; Mw = 2000 - 3000) 50 The test of EXAMPLE 1 is repeated using different powdered primers, the composition of which comprises (in grams): EXAMPLE 2.A - epoxy resin obtained by reaction of epichlorohydrin and bisphenol A. (molecular mass: 1400 g; weight of epoxide equivalent: 850-950; softening point: 90 ° C) 90 - catalyzed or micronized dicyandiamide resin 10 EXAMPLE 2.B - epoxy resin with the same characteristics as in 2.A 92.5 - phthalic anhydride 7.5 EXAMPLE 2.C - epoxy resin with the same characteristics as in 2.A 92 - diamino diphenylsulfone 8 EXAMPLE 2.D - epoxy resin with the same characteristics as in 2.A 50 - saturated polyester resin (acid number: 70-85; Tg = 55 ° C) 50 EXAMPLE 2.E - epoxy resin with the same characteristics as in 2.A 50 - phenol / aldehyde resin (melting point: 100 ° C; aldehyde / phenol: 1.2 (in M); Mw = 2000 - 3000) 50

Le substrat métallique est une plaque d'acier sablé et le revête­ment superficiel a les mêmes caractéristiques que celles de l'EXEMPLE 1.The metal substrate is a sandblasted steel plate and the surface coating has the same characteristics as those of EXAMPLE 1.

Le substrat est revêtu du primaire par projection électrostatique dans les mêmes conditions qu'en 1.B.The substrate is coated with the primer by electrostatic spraying under the same conditions as in 1.B.

Il passe ensuite dans un four maintenu à 330°C où il séjourne pendant 10 mn.It then passes into an oven maintained at 330 ° C where it remains for 10 minutes.

Immédiatement après, il est immergé dans une cuve de trempage en lit fluidisé dans les mêmes conditions que celles décrites en 1.B.Immediately afterwards, it is immersed in a soaking tank in a fluidized bed under the same conditions as those described in 1.B.

Le matériau obtenu est un composite comprenant successivement :
- une plaque d'acier sablé (épaisseur 3 mm)
- une couche de primaire d'épaisseur moyenne égale à 20 µm
- une couche de revêtement superficiel d'épaisseur comprise entre 200 et 250 µm.The material obtained is a composite comprising successively:
- a sandblasted steel plate (thickness 3 mm)
- a primer layer of average thickness equal to 20 µm
- a surface coating layer of thickness between 200 and 250 µm.

Les matériaux subissent un test d'adhérence réalisé selon la norme NF T 58-112 et un test de vieillissement au brouillard salin réalisé selon la norme NF X 41-002.The materials undergo an adhesion test carried out according to standard NF T 58-112 and a salt spray aging test carried out according to standard NF X 41-002.

Les résultats sont réunis dans le Tableau I.The results are collated in Table I.

EXEMPLE 3EXAMPLE 3

On renouvelle l'essai de l'EXEMPLE 1 en utilisant un primaire en poudre qui comprend (en g). A) - résine époxyde modifiée novolaque (poids d'équivalent époxyde : 500-575 ; point de ramollissement compris entre 90 et 98°C ; d = 1,19) 92 - dicyandiamide micronisée 8 B) - poly p. vinylphénol de Mw compris entre 2000 et 30000, de poids d'équivalent époxyde = 120 et possédant un poids de ramollissement compris entre 140 et 210°C. 100 The test of EXAMPLE 1 is repeated using a powdered primer which comprises (in g). A) - modified novolak epoxy resin (epoxy equivalent weight: 500-575; softening point between 90 and 98 ° C; d = 1.19) 92 - micronized dicyandiamide 8 B) - poly p. vinylphenol Mw between 2000 and 30000, of epoxy equivalent weight = 120 and having a softening weight between 140 and 210 ° C. 100

Le substrat métallique et le revêtement superficiel ont les mêmes caractéristiques que dans l'EXEMPLE 2 et les conditions de mise en oeuvre et d'évaluation des matériaux obtenus sont identiques à celles décrites dans l'EXEMPLE 2.The metal substrate and the surface coating have the same characteristics as in EXAMPLE 2 and the conditions for placing work and evaluation of the materials obtained are identical to those described in EXAMPLE 2.

Les résultats obtenus sont réunis dans le Tableau I.The results obtained are collated in Table I.

EXEMPLE 4 (COMPARATIF) EXAMPLE 4 (COMPARATIVE)

On renouvelle l'essai de l'EXEMPLE 1 en utilisant un primaire liquide qui comprend les résines suivantes :
- résine époxyde obtenue par réaction de l'épichlorhydrine et du bisphénol A dont la masse moléculaire est comprise entre 3000 et 3800 g et le poids d'équivalent époxyde entre 1600 et 4000.
- résine formo-phénolique de type résol
- résine aminoplaste mélamine-formol
en solution dans un mélange d'éthylèneglycol, solvant naphta, butanol, isobutanol et méthylisobutyl-cétone.The test of EXAMPLE 1 is repeated using a liquid primer which comprises the following resins:
- epoxy resin obtained by reaction of epichlorohydrin and bisphenol A whose molecular mass is between 3000 and 3800 g and the weight of epoxide equivalent between 1600 and 4000.
- resol phenophenol type resin
- aminoplast melamine-formaldehyde resin
dissolved in a mixture of ethylene glycol, solvent naphtha, butanol, isobutanol and methyl isobutyl ketone.

Le substrat métallique et le revêtement superficiel ont les mêmes caractéristiques que ceux de l'EXEMPLE 1.The metal substrate and the surface coating have the same characteristics as those of EXAMPLE 1.

Les conditions de mise en oeuvre sont identiques à celles décrites en 1.B.The conditions of implementation are identical to those described in 1.B.

Le matériau obtenu est tel que l'adhérence initiale du revêtement est nulle (Classe O) et le cheminement à la corrosion est total en quelques heures.The material obtained is such that the initial adhesion of the coating is zero (Class O) and the corrosion path is complete in a few hours.

EXEMPLE 5 (COMPARATIF) EXAMPLE 5 (COMPARATIVE)

On renouvelle l'essai de l'EXEMPLE 1 en utilisant le primaire décrit en 2A dans les conditions opératoires décrites dans la demande de brevet Français N° 2 340 140.The test of EXAMPLE 1 is repeated using the primer described in 2A under the operating conditions described in French patent application No. 2,340,140.

Soit la succession des étapes suivantes :
- Application au pistolet électrostatique (V = - 40 kV) du primaire (épaisseur = 100 µm) sur une plaque d'acier sablé d'épaisseur 1 mm.
- Chauffage de la plaque recouverte de poudre à 200°C pendant 3 mm.
- Application du polyamide-11 après refroissement de la plaque par projection électrostatique (V =-40 kV) Epaisseur≃140 µm.
- Post-fusion du système à 300°C pendant 3 mn.Or the succession of the following stages:
- Application with an electrostatic gun (V = - 40 kV) of the primer (thickness = 100 µm) on a sanded steel plate 1 mm thick.
- Heating of the plate covered with powder at 200 ° C for 3 mm.
- Application of polyamide-11 after cooling the plate by electrostatic spraying (V = -40 kV) Thickness≃140 µm.
- Post-fusion of the system at 300 ° C for 3 min.

On obtient ainsi un revêtement bi-couche comprenant
- une sous-couche époxyde (42 % de l'épaisseur totale du revêtement)
- une couche de polyamide, l'épaisseur totale du revêtement étant égale à 260 µm.A two-layer coating is thus obtained comprising
- an epoxy undercoat (42% of the total thickness of the coating)
- a polyamide layer, the total thickness of the coating being equal to 260 μm.

Les résultats obtenus aux tests d'adhérence et de vieillissement au brouillard salin sont donnés dans le tableau I.The results obtained in the salt spray adhesion and aging tests are given in Table I.

L'aspect de surface du revêtement est assez mauvais avec en particulier un bullage sur les bords correspondant à une dégradation du primaire. TABLEAU I No d'EX EX 2A EX 2B EX 2C EX 2D EX 2E EX 3A EX 3B EX 5 Adhérence t = 0 3-4 4 3 3 4 4 3-4 3 Adhérence après 1500 h B.S. 3-4 2 3 2 3-4 2 3 0 Cheminement B.S. 7 10 4 13 7 10 5 Décollement total dès 500h Cloquage 1500 h 10 8M 10 8M 10 10 10 - B.S. = brouillard salin The surface appearance of the coating is quite poor with in particular bubbling on the edges corresponding to degradation of the primer. TABLE I EX # EX 2A EX 2B EX 2C EX 2D EX 2E EX 3A EX 3B EX 5 Adhesion t = 0 3-4 4 3 3 4 4 3-4 3 Grip after 1500 hrs BS 3-4 2 3 2 3-4 2 3 0 BS path 7 10 4 13 7 10 5 Total detachment from 500h Blistering 1500 h 10 8M 10 8M 10 10 10 - BS = salt spray

Claims (6)

1. Procédé pour revêtir des substrats métalliques à l'aide d'un primaire d'adhérence et d'un revêtement superficiel, caractérisé en ce qu'il comprend les étapes suivantes : a) enduction du substrat avec une ou plusieurs couches de primaire d'adhérence en poudre à base de résines thermodurcissables selon une technique d'application en poudre, b) chauffage du substrat ainsi revêtu et immédiatement après : c) application par trempage en lit fluidisé du revêtement superficiel en poudre. 1. Method for coating metallic substrates using an adhesion primer and a surface coating, characterized in that it comprises the following steps: a) coating of the substrate with one or more layers of powder adhesion primer based on thermosetting resins according to a powder application technique, b) heating the substrate thus coated and immediately after: c) application by soaking in a fluidized bed of the surface powder coating. 2. Procédé selon la revendication 1, caractérisé en ce que la température de chauffage du substrat de l'étape b) peut atteindre 380°C.2. Method according to claim 1, characterized in that the heating temperature of the substrate of step b) can reach 380 ° C. 3. Procédé selon la revendication 1 ou 2 dans lequel le revêtement superficiel est à base de polyamide, de préférence de PA-11 et/ou de PA-12, et/ou à base de polyétheresteramide.3. Method according to claim 1 or 2 wherein the surface coating is based on polyamide, preferably PA-11 and / or PA-12, and / or based on polyetheresteramide. 4. Composition de primaire d'adhérence en poudre à base de résine(s) époxydes et de durcisseur(s) de résine(s) époxyde(s) mise en oeuvre dans le procédé tel que défini dans la revendication 1, 2 ou 3.4. Composition of powder adhesion primer based on epoxy resin (s) and epoxy resin hardener (s) used in the process as defined in claim 1, 2 or 3 . 5. Composition selon la revendication 4, caractérisée en ce que les durcisseurs de résine(s) époxyde(s) sont choisis parmi les résines de type amine, anhydride d'acide ou isocyanate.5. Composition according to claim 4, characterized in that the epoxy resin hardeners are chosen from resins of amine, acid anhydride or isocyanate type. 6. Matériaux composites constitués :
- d'un substrat métallique,
- d'une ou plusieurs couches de primaire d'adhérence tel que défini dans les revendications 1 à 5, d'épaisseur moyenne de préférence comprise entre 10 et 20 µm,
- d'un revêtement superficiel tel que défini dans les reven­dications 1 à 3, d'épaisseur moyenne de préférence comprise entre 200 et 400 µm.6. Composite materials made up:
- a metallic substrate,
- one or more layers of adhesion primer as defined in claims 1 to 5, of average thickness preferably between 10 and 20 µm,
- a surface coating as defined in claims 1 to 3, of average thickness preferably between 200 and 400 µm.
EP89402897A 1988-11-03 1989-10-20 Method of coating metal substrates with a powder primer and a surface coat applied by dipping and product obtained Expired - Lifetime EP0367653B2 (en)

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Application Number Priority Date Filing Date Title
FR8814332A FR2638466B1 (en) 1988-11-03 1988-11-03 PROCESS FOR COATING METAL SUBSTRATES USING A POWDER PRIMER AND A DIP APPLIED COATING, POWDER PRIMER COMPOSITIONS USED AND COMPOSITE MATERIALS OBTAINED
FR8814332 1988-11-03

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EP0367653A1 true EP0367653A1 (en) 1990-05-09
EP0367653B1 EP0367653B1 (en) 1993-05-19
EP0367653B2 EP0367653B2 (en) 2001-11-21

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DK (1) DK174338B1 (en)
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WO2006091440A1 (en) * 2005-02-23 2006-08-31 Ppg Industries Ohio, Inc. Methods of forming composite coatings
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JP5721330B2 (en) * 2010-01-27 2015-05-20 藤倉化成株式会社 Base coat coating composition, composite coating film and method for producing the same
JP5606807B2 (en) * 2010-06-14 2014-10-15 中央発條株式会社 Powder coating method
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WO1997037776A1 (en) * 1996-04-08 1997-10-16 E.I. Du Pont De Nemours And Company Process for coating a substrate
WO2000076677A1 (en) * 1999-06-15 2000-12-21 Atofina Method for covering an object with a film and equipment implementing said method
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Also Published As

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IE63336B1 (en) 1995-04-19
EP0367653B2 (en) 2001-11-21
ES2055133T5 (en) 2002-05-01
PT92182B (en) 2001-05-31
FI895222A0 (en) 1989-11-02
DK546089D0 (en) 1989-11-02
FR2638466A1 (en) 1990-05-04
DK174338B1 (en) 2002-12-16
US5891515A (en) 1999-04-06
ES2055133T3 (en) 1994-08-16
EP0367653B1 (en) 1993-05-19
NO894344L (en) 1990-05-04
JPH02258084A (en) 1990-10-18
CA2002109C (en) 1999-02-16
AU4397989A (en) 1990-05-10
ATE89496T1 (en) 1993-06-15
DK546089A (en) 1990-05-04
AU628877B2 (en) 1992-09-24
FI100661B (en) 1998-01-30
DE68906643T2 (en) 1993-10-07
NO306956B1 (en) 2000-01-17
DE68906643T3 (en) 2002-05-29
PT92182A (en) 1990-05-31
DE68906643D1 (en) 1993-06-24
NO894344D0 (en) 1989-11-01
CA2002109A1 (en) 1990-05-03
FR2638466B1 (en) 1993-05-07
IE893536L (en) 1990-05-03
JPH0755306B2 (en) 1995-06-14

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