EP0141796A1 - Process for applying cured resin coatings to substrates - Google Patents

Process for applying cured resin coatings to substrates Download PDF

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Publication number
EP0141796A1
EP0141796A1 EP84870138A EP84870138A EP0141796A1 EP 0141796 A1 EP0141796 A1 EP 0141796A1 EP 84870138 A EP84870138 A EP 84870138A EP 84870138 A EP84870138 A EP 84870138A EP 0141796 A1 EP0141796 A1 EP 0141796A1
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EP
European Patent Office
Prior art keywords
resin
substrate
coating film
film
coating
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.)
Withdrawn
Application number
EP84870138A
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German (de)
French (fr)
Inventor
G.R. Svoboda
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UCB SA
Original Assignee
UCB SA
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Filing date
Publication date
Application filed by UCB SA filed Critical UCB SA
Publication of EP0141796A1 publication Critical patent/EP0141796A1/en
Withdrawn legal-status Critical Current

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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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • B05D1/286—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers using a temporary backing to which the coating has been applied
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0209—Multistage baking
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/068—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using ionising radiations (gamma, X, electrons)
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B05D3/0263—After-treatment with IR heaters
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B05D3/0272—After-treatment with ovens

Definitions

  • the present invention relates to the technique of coated substrates, and, in particular, to the technique of coating substrates with resins cured by exposure to an electron beam or to ultraviolet radiation.
  • Adhesion problems can result from many factors, such as the shrinkage of the coating after drying or hardening or the incompatibility of the two materials.
  • a first object of the present invention is to provide a method for applying to a substrate a coating of synthetic resin hardened by an electron beam or by ultraviolet radiation.
  • Another object of the present invention is to provide a coated article with improved adhesion between the coating and the substrate.
  • a further object of the present invention is to provide a coating method which involves the use of the speed of curing by an electron beam or by ultraviolet radiation, but which avoids the problems of shrinkage and / or relaxation tension and leads to improved grip.
  • a sheet of uncured synthetic resin of the type which can be cured by exposure to an electron beam or ultraviolet radiation is preferably supported on at least one side by a release sheet of poly (ethylene terephthalate) or any other suitable material.
  • the sheet can be prepared in the form of a roll or sheet.
  • the carrier sheets improve handling of the flexible, solid, uncured resin sheet and further protect the resin sheet from contact with air during the electron beam or radiation curing stage .
  • the process of the present invention comprises the initial fixing of the uncured sheet to the substrate to be coated, a stage of the process which can be carried out in different ways but which is preferably carried out by heating the uncured sheet and applying pressure to form an initial joint.
  • the bottom sheet is removed before the adhesion stage.
  • the combined materials are then exposed to an electron beam or ultraviolet light to harden the resin sheet. This is typically done with the top sheet in place. After this curing stage, the top sheet is removed from the resin sheet-substrate combination.
  • Variants of the present invention will appear to those skilled in the art after reading the description which follows. Some will be immediately recognized, such as the use of clear, loaded, pigmented, non-pigmented or embossed sheets. Others may not be recognized immediately, but are considered to fall within the scope of the present invention if they follow these general teachings and fall under the guise of the claims which follow the description of the preferred embodiment.
  • Figure 1 is illustrated the method according to the preferred embodiment of the present invention.
  • the product to be prepared by the process is a rolled steel sheet coated with resin.
  • a first coil 10 of sheet material 12 is shown, this material comprising three separate layers 13-15.
  • Layers 13 and 15 form the top and bottom of a resin sandwich and include clear sheets of peelable backing films.
  • the preferred material to be used is poly (ethylene terephthalate), but other peelable support films known in the art can also be used, for example, thermoplastic films such as polyvinyl chloride , polyethylene or polyvinyl acetate.
  • the figures illustrate a process in which the support films 13 and 15 are removed mechanically, that is to say by skinning, but it is obvious to a person skilled in the art that films of the washable type, such as polyvinyl acetate could be used for one or both support films. Obviously, in such a case, the process would be modified to provide washing stations in place of the take-up rollers which will be described shortly in the description.
  • the central layer 14 of the sheet material 12 is a layer of resin curable by an electron beam or ultraviolet radiation, which is solid at temperatures below about 10-32 ° C, i.e. temperatures commonly encountered in the environment of coating processes.
  • the layer 14 must melt at high temperatures, such as for example a resin designated in English technical language by the term "hot-melt".
  • a resin designated in English technical language by the term "hot-melt" The particular type of resin to be used for layer 14 is not critical to the present invention provided that it meets the above criteria.
  • a preferred type of material is that described in US Patent 4,078,015 issued March 7, 1978 to Leitheiser and Szwarc entitled “Copolymerizable Compositions and Method of Making the Same". The description of this patent is expressly incorporated here by this reference.
  • the resins of the Leitheiser patent comprise at least two monomers, each having at least one acrylic terminal group and each containing at least two internal urethane bonds.
  • a resin of this kind comprises a first acrylic diurethane monomer and a second polyacrylic polyurethane monomer prepared from an organic diisocyanate, a beta-hydroxy alkyl ester of an acrylic acid and a vi. Suitable reagents and suitable methods for preparing the resins are described in the aforementioned patent, a further description of these will therefore not be necessary here.
  • the sheet material 12 can be prepared by techniques known per se, but in the preferred embodiment it is prepared by melting an amount of the resin for layer 14 and applying it uniformly on the lower layer 13 A release coating (not shown) can be applied to layer 13 before that the resin layer 14 is applied. The molten resin is allowed to cool and the upper layer 15 is applied thereto (with or without a release coating as mentioned above).
  • the carrier films 13 and 15 serve several practical uses in the present invention. Firstly, by using two layers, the sheet material 12 can be rolled up or unwound easily from the reel 10. At this point it should also be mentioned that if the layer 14 is sufficiently free of cold tack, the lower layer 13 can be eliminated.
  • the second reason why a support for the resin layer 14 is preferred is that many resins curable by an electron beam or ultraviolet radiation are sensitive to exposure to air, both during storage and especially during the curing process. If layer 14 is sensitive to exposure during storage, both layers 13 and 15 should be used at the same time. If the sensitivity occurs mainly during curing, the lower support layer 13 can be removed.
  • the adhesion between the carrier films and layer 14 should be sufficient to allow proper handling and storage of the resin sandwich but should not be as great as to cause physical damage to layer 14 when the carrier films are removed from them.
  • the first stage in the process of the invention consists in removing the layer 13 from the sheet material 12, which is carried out in FIG. 1 using the take-up roller 17.
  • a free roll 18 is placed near the reel 10 and the layer 13 passes around it and towards the roller 17.
  • Another feed roller 20 contains a steel roller 22, which is to be coated by the process of the present invention.
  • a pair of free rollers 23 is located near but spaced from the roller 18, the lower layer 13 thus being, in fact, replaced by the steel 22 as part of a sandwich 25 which exists downstream of the rollers 18 and 23 .
  • a work surface 30 is shown in Figure 1, which can take any suitable shape known in the coating art, such as spaced parallel transport rollers or a smooth work table. Since the support surface itself is not part of the present invention, details thereof have been omitted in the figures.
  • the next step in the process of the invention is to form an initial seal between the resin layer 14 and the steel 22.
  • this is done by passing the layers 14 and 15 and the steel 22 by the heating chamber 26 where the components are heated above the melting temperature of the layer 14 to soften the latter.
  • the chamber 26 is shown as containing a plurality of heating elements 36 disposed above and below the sheets.
  • the elements 36 can be resistance type radiators, infrared lamps, etc.
  • the drawings are generally in schematic form and are not intended to limit the present invention. Other heating techniques can be used, such as for example the use of heated rollers touching one or both sheets.
  • the layer 14 is made to adhere to the steel 22, for example by passing the assembly between a pair of pressure rollers 40. At this stage of the process, a new three-component sandwich 41 is formed.
  • the roll material to be coated can be provided with a primer or include a film of a bonding coating (not shown), if desired to improve the adhesion between layer 14 and the roll material. 22.
  • a primer or include a film of a bonding coating (not shown), if desired to improve the adhesion between layer 14 and the roll material. 22.
  • suitable primers or tack coatings there may be mentioned epoxy esters, epoxy compounds cured by aminoplasts and / or epoxy resins cured by polyamides or amines.
  • a resin sandwich has been prepared, but the resin layer 14 is still in the uncured state.
  • the sandwich is exposed to an electron beam or to actinic ultraviolet radiation in chamber 42. The exposure takes place through the upper layer 15, the layer 14 being thus protected from the exposure to air during the curing stage.
  • apparatuses are commercially available for effecting curing by an electron beam or by ultraviolet radiation of sheet materials, but preferred apparatuses for use in the practice of the present invention are the units curing by ultraviolet irradiation equipped with mercury vapor lamps, such as the 18H model manufactured by Ashdee Corp. or linear or scanning cathode electron accelerators such as those manufactured by Energy Sciences Inc. or Radiation Polymer Corp.
  • a complete curing of a urethane-acrylate "hot melt” resin can be carried out in a thickness of 127, 381 or 762 Y m at a speed 15.24 m / min.
  • the upper layer 15 is poly (ethylene terephthalate) of 127 rm and the roll material 22 is sheet steel provided with a primer of vinyl acetate-vinyl chloride copolymer.
  • the final stage of the process of the present invention comprises removing the top sheet 15. This is done by pulling the sheet around another free roll 43 and winding the top sheet 15 around the take-up reel 44.
  • the carrier sheets can be discarded, reused in the process or recycled.
  • the present invention provides a coated substrate with an adhesion between the coating and the substrate which is greater than that obtained by applying coatings of similar types in the liquid state and using curing by an electron beam or by radiation. ultraviolet.
  • the adhesion of the coated article made up in the example cited above was 100% by the test method on cross cuts and peeling of a ribbon ("cross hatch and tape pull method "compared to 0-25% adhesion using the same test method when a coated article was prepared by applying a liquid film of a vinyl ester resin as claimed in US Patent 4,216 .306, in a thickness of 127, 381 or 762 rm on steel provided with a similar primer with hardening carried out by an Ashdee hardening apparatus and a running speed of 15.24 m / min.
  • FIG. 3 A modification would be to use a resin layer 14 supported on the upper face as shown in FIG. 3.
  • the process is identical to that of FIG. 1, except that the free roller 18 and the take-up roller 17 are eliminated.
  • a layer of primer 45 is shown as being applied to the material 22 before it passes through the rollers 23.
  • the sandwich formed in this embodiment is shown in FIG. 4 above the table working 30.
  • FIG. 5 Another modification is shown in FIG. 5 in which the layer 14 is pigmented at 46 in a decorative manner before the application to the roll material 22.
  • the resin layer 14 serving as coating can be colored, pigmented or embossed in any desired pattern.

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  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
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Abstract

A film of uncured synthetic resin is used for the coating of metals, a piece of paper, a fabric or synthetic materials. The resin employed can be cured by exposure to ultraviolet radiation or to a beam of electrons; it is solid in the uncured state at temperatures below approximately 10-32 DEG C. The film is applied to a substrate which is or is not provided with a primer, and bonded to the substrate by heating and the application of pressure. The substrate coated with the film of resin is then exposed to a beam of electrons or to ultraviolet radiation in order to cure the film. When a supported film is used, the support film is placed on the upper face of the film of resin in order to protect it from exposure to air during the curing, and it is removed from the cured film in order to obtain the final desired product.

Description

La présente invention se rapporte à la technique des substrats enduits, et, en particulier, à la technique de revêtement de substrats avec des résines durcies par exposition à un faisceau d'électrons ou à un rayonnement ultraviolet.The present invention relates to the technique of coated substrates, and, in particular, to the technique of coating substrates with resins cured by exposure to an electron beam or to ultraviolet radiation.

On connaît une grande variété de techniques pour le revêtement de substrats tels que du papier, des films, du métal, etc. Un problème fréquemment rencontré dans ce domaine est l'obtention d'une adhérence suffisante entre le substrat et le revêtement appliqué. Des problèmes d'adhérence peuvent résulter de nombreux facteurs, comme le retrait de l'enduit après séchage ou durcissement ou encore l'incompatibilité des deux matériaux.A wide variety of techniques are known for coating substrates such as paper, films, metal, etc. A problem frequently encountered in this area is obtaining sufficient adhesion between the substrate and the coating applied. Adhesion problems can result from many factors, such as the shrinkage of the coating after drying or hardening or the incompatibility of the two materials.

Il a été proposé récemment de revêtir des substrats métalliques avec des résines liquides durcissables par un faisceau d'électrons ou par un rayonnement ultraviolet, mais le développement de ce concept a été entravé par le manque d'adhérence qui est associé en général avec les revêtements durcis par un faisceau d'électrons. Etant donné que le durcissement par un faisceau d'électrons est quasi instantané, on croit qu'il n'y a pas de temps suffisant pour qu'il se produise une relaxation des tensions lorsque le revêtement est appliqué sur le métal. Ceci est probablement dû au retrait qui se produit pendant la transition de l'état liquide à l'état solide et celui associé à une diminution du nombre de double liaisons pendant le processus de durcissement. Par conséquent, ce concept plein de promesses n'a pas été commercialisé sur une grande échelle.It has recently been proposed to coat metallic substrates with liquid resins curable by an electron beam or by ultraviolet radiation, but the development of this concept has been hampered by the lack of adhesion which is generally associated with coatings. hardened by an electron beam. Since the hardening by an electron beam is almost instantaneous, it is believed that there is not enough time for a relaxation of the tensions when the coating is applied to the metal. This is likely due to the shrinkage that occurs during the transition from the liquid to the solid state and that associated with a decrease in the number of double bonds during the curing process. Therefore, this concept full of promise has not been marketed on a large scale.

Ces défauts sont décevants, parce que le durcissement par un faisceau d'électrons présente beaucoup d'autres avantages attrayants dans la technique de revêtement, comme par exemple des vitesses beaucoup plus élevées que celles qui sont possibles avec des systèmes basés sur des solvants ou thermodurcissables. Ces derniers systèmes présentent également des problèmes d'adhérence dus au manque de relaxation suffisante des tensions pendant la mise en liberté du solvant et le refroidissement du revêtement échauffé. Un procédé de revêtement de substrats avec des résines durcissables par un faisceau d'électrons ou par un rayonnement ultraviolet qui procure une adhérence accrue entre le revêtement et le substrat serait très souhaitable et présenterait un progrès important dans la technique de revêtement.These defects are disappointing, because curing by an electron beam has many other attractive advantages in the coating technique, such as much higher speeds than those possible with solvent-based or thermosetting systems. . These latter systems also have adhesion problems due to the lack of sufficient tension relaxation during the release of the solvent and the cooling of the heated coating. A method of coating substrates with resins curable by an electron beam or by ultraviolet radiation which provides increased adhesion between the coating and the substrate would be highly desirable and would show significant progress in the coating technique.

Un premier objet de la présente invention est de procurer un procédé pour appliquer sur un substrat un revêtement de résine synthétique durcie par un faisceau d'électrons ou par un rayonnement ultraviolet.A first object of the present invention is to provide a method for applying to a substrate a coating of synthetic resin hardened by an electron beam or by ultraviolet radiation.

Un autre objet de la présente invention est de procurer un article enduit avec une adhérence améliorée entre le revêtement et le substrat.Another object of the present invention is to provide a coated article with improved adhesion between the coating and the substrate.

Un objet supplémentaire de la présente invention est de procurer un procédé de revêtement qui comprend l'utilisation d'une feuille non durcie solide de résine synthétique comme matière de revêtement.It is a further object of the present invention to provide a coating method which comprises using a solid uncured sheet of synthetic resin as a coating material.

Un objet supplémentaire de la présente invention est de procurer un procédé de revêtement qui comporte l'usage de la vitesse d'un durcissement par un faisceau d'électrons ou par un rayonnement ultraviolet, mais qui évite les problèmes de retrait et/ou de relaxation des tensions et conduit à une adhérence améliorée.A further object of the present invention is to provide a coating method which involves the use of the speed of curing by an electron beam or by ultraviolet radiation, but which avoids the problems of shrinkage and / or relaxation tension and leads to improved grip.

Dans la description qui suit, pris conjointement avec les dessins, il sera décrit comment ces objets et d'autres objets de l'invention sont réalisés. En général toutefois, ces objets sont réalisés en utilisant une feuille de résine synthétique non durcie du type qui peut être durcie par exposition à un faisceau d'électrons ou à un rayonnement ultraviolet. La feuille est de préférence supportée sur au moins une face par une feuille détachable de poly(téréphtalate d'êthylëne) ou un autre matériau approprié quelconque. La feuille peut être préparée sous forme de rouleau ou de'feuille. Les feuilles de support améliorent la manipulation de la feuille de résine flexible, solide, non durcie et, en outre, elles protègent la feuille de résine d'un contact avec l'air pendant le stade de durcissement par faisceau d'électrons ou par rayonnement. Le procédé de la présente invention comprend la fixation initiale de la feuille non durcie au substrat à revêtir, un stade du procédé qui peut être exécuté de différentes manières mais qui est de préférence réalisé par chauffage de la feuille non durcie et en appliquant une pression pour former un joint initial. Lorsque la feuille non durcie a été revêtue de deux feuilles de support, la feuille inférieure est enlevée avant le stade d'adhésion. Les matériaux combinés sont ensuite exposés à un faisceau d'électrons ou a la lumière ultraviolette pour durcir la feuille de résine. Ceci est effectué typiquement avec la feuille supérieure en place. Après ce stade de durcissement, la feuille supérieure est enlevée de la combinaison feuille de résine- substrat. Des variantes de la présente invention apparaîtront à l'homme de métier après lecture de la description qui suit. Certaines seront immédiatement reconnues, comme par exemple l'utilisation de feuilles claires, chargées, pigmentées, non pigmentées ou gaufrées. D'autres peuvent ne pas être reconnues immédiatement, mais sont considérées comme tombant dans le cadre de la présente invention si elles suivent ces enseignements généraux et tombent sous le couvert des revendications qui suivent la description de la forme de réalisation préférée.In the following description, taken in conjunction with the drawings, it will be described how these and other objects of the invention are achieved. In general, however, these objects are made using a sheet of uncured synthetic resin of the type which can be cured by exposure to an electron beam or ultraviolet radiation. The sheet is preferably supported on at least one side by a release sheet of poly (ethylene terephthalate) or any other suitable material. The sheet can be prepared in the form of a roll or sheet. The carrier sheets improve handling of the flexible, solid, uncured resin sheet and further protect the resin sheet from contact with air during the electron beam or radiation curing stage . The process of the present invention comprises the initial fixing of the uncured sheet to the substrate to be coated, a stage of the process which can be carried out in different ways but which is preferably carried out by heating the uncured sheet and applying pressure to form an initial joint. When the uncured sheet has been coated with two backing sheets, the bottom sheet is removed before the adhesion stage. The combined materials are then exposed to an electron beam or ultraviolet light to harden the resin sheet. This is typically done with the top sheet in place. After this curing stage, the top sheet is removed from the resin sheet-substrate combination. Variants of the present invention will appear to those skilled in the art after reading the description which follows. Some will be immediately recognized, such as the use of clear, loaded, pigmented, non-pigmented or embossed sheets. Others may not be recognized immediately, but are considered to fall within the scope of the present invention if they follow these general teachings and fall under the guise of the claims which follow the description of the preferred embodiment.

Dans les dessins d'accompagnement:

  • la figure 1 représente schématiquement le procédé selon la forme de réalisation préférée de l'invention où la feuille de résine est supportée sur les deux faces par une feuille détachable de film protecteur;
  • la figure 2 est une coupe selon la ligne II-II de la figure 1;
  • la figure 3 représente schématiquement le procédé selon la forme de réalisation préférée de la présente invention où la feuille de résine est supportée sur la face supérieure par une feuille détachable de film protecteur;
  • la figure 4 est une coupe selon la ligne IV-IV de la figure 3;
  • la figure 5 est une vue en plan du haut d'une feuille de résine selon la présente invention dans laquelle la feuille est pigmentée de manière décorative.
In the accompanying drawings:
  • Figure 1 schematically shows the method according to the preferred embodiment of the invention wherein the resin sheet is supported on both sides by a removable sheet of protective film;
  • Figure 2 is a section along the line II-II of Figure 1;
  • FIG. 3 schematically represents the method according to the preferred embodiment of the present invention in which the resin sheet is supported on the upper face by a detachable sheet of protective film;
  • Figure 4 is a section along the line IV-IV of Figure 3;
  • Figure 5 is a top plan view of a resin sheet according to the present invention in which the sheet is decoratively pigmented.

Dans la figure 1 est illustré le procédé selon la forme de réalisation préférée de la présente invention. Le produit à préparer par le procédé est une feuille d'acier en rouleau revêtue de résine.In Figure 1 is illustrated the method according to the preferred embodiment of the present invention. The product to be prepared by the process is a rolled steel sheet coated with resin.

Dans cette figure, on montre une première bobine 10 de matière 12 en feuille, cette matière comprenant trois couches séparées 13-15. Les couches 13 et 15 constituent le dessus et le dessous d'un sandwich de résine et comprennent des feuilles claires de films de support détachables. Pour les couches 13 et 15 le matériau préféré à utiliser est le poly(téréphtalate d'éthylène), mais d'autres films de support détachables connus dans la technique peuvent aussi être employés, par exemple, des films thermoplastiques tels que le chlorure de polyvinyle, le polyéthylène ou l'acétate de polyvinyle. Il faut mentionner ici également que les figures illustrent un procédé dans lequel les films de support 13 et 15 sont enlevés mécaniquement, c'est-â-dire par dépouillage, mais il est évident pour un homme du métier que des films du type lavable, tels que l'acétate de polyvinyle pourraient être utilisés pour un ou pour les deux films de support. Evidemment, dans un cas pareil, le procédé serait modifié pour prévoir des stations de lavage en lieu et place des rouleaux récepteurs qui seront sous peu décrits dans la description.In this figure, a first coil 10 of sheet material 12 is shown, this material comprising three separate layers 13-15. Layers 13 and 15 form the top and bottom of a resin sandwich and include clear sheets of peelable backing films. For layers 13 and 15 the preferred material to be used is poly (ethylene terephthalate), but other peelable support films known in the art can also be used, for example, thermoplastic films such as polyvinyl chloride , polyethylene or polyvinyl acetate. It should also be mentioned here that the figures illustrate a process in which the support films 13 and 15 are removed mechanically, that is to say by skinning, but it is obvious to a person skilled in the art that films of the washable type, such as polyvinyl acetate could be used for one or both support films. Obviously, in such a case, the process would be modified to provide washing stations in place of the take-up rollers which will be described shortly in the description.

La couche centrale 14 de la matière 12 en feuille est une couche de résine durcissable par un faisceau d'électrons ou un rayonnement ultraviolet, qui est solide à des températures inférieures à environ 10-32°C, c'est-à-dire les températures communément rencontrées dans l'environnement de procédés de revêtement.The central layer 14 of the sheet material 12 is a layer of resin curable by an electron beam or ultraviolet radiation, which is solid at temperatures below about 10-32 ° C, i.e. temperatures commonly encountered in the environment of coating processes.

La couche 14 doit fondre à des températures élevées, comme par exemple une résine désignée dans le langage technique anglo-saxon par le terme "hot-melt". Le type particulier de résine à employer pour la couche 14 n'est pas critique pour la présente invention pourvu qu'il satisfasse aux critères précédents. Un type préféré de matériau est celui décrit dans le brevet américain 4.078.015 délivré le 7 mars 1978 à Leitheiser et Szwarc intitulé "Copolymerizable Compositions and Method of Making the Same". La description de ce brevet est expressément incorporée ici par cette référence.The layer 14 must melt at high temperatures, such as for example a resin designated in English technical language by the term "hot-melt". The particular type of resin to be used for layer 14 is not critical to the present invention provided that it meets the above criteria. A preferred type of material is that described in US Patent 4,078,015 issued March 7, 1978 to Leitheiser and Szwarc entitled "Copolymerizable Compositions and Method of Making the Same". The description of this patent is expressly incorporated here by this reference.

Les résines du brevet Leitheiser comprennent au moins deux monomères, ayant chacun au moins un groupe terminal acrylique et contenant chacun au moins deux liaisons uréthane intérieures. Une résine de ce genre comprend un premier monomère diuréthane acrylique et un second monomère polyuréthane polyacrylique préparé à partir d'un diisocyanate organique, d'un ester alkylique bêta-hydroxylé d'un acide acrylique et d'un vi. Des réactifs appropriés et des méthodes appropriées pour préparer les résines sont décrits dans le brevet précité, une description complémentaire de ceux-ci ne sera donc pas nécessaire ici.The resins of the Leitheiser patent comprise at least two monomers, each having at least one acrylic terminal group and each containing at least two internal urethane bonds. A resin of this kind comprises a first acrylic diurethane monomer and a second polyacrylic polyurethane monomer prepared from an organic diisocyanate, a beta-hydroxy alkyl ester of an acrylic acid and a vi. Suitable reagents and suitable methods for preparing the resins are described in the aforementioned patent, a further description of these will therefore not be necessary here.

La matière 12 en feuille peut être préparée par des techniques connues en soi, mais dans la forme de réalisation préférée elle est préparée en faisant fondre une quantité de la résine pour la couche 14 et en l'appliquant de manière uniforme sur la couche inférieure 13. Un enduit de démoulage (non représent) peut être appliqué sur la couche 13 avant que la couche de résine 14 est appliquée. On laisse refroidir la résine fondue et la couche supérieure 15 est appliquée sur celle-ci (avec ou sans un enduit de démoulage comme mentionné précédemment).The sheet material 12 can be prepared by techniques known per se, but in the preferred embodiment it is prepared by melting an amount of the resin for layer 14 and applying it uniformly on the lower layer 13 A release coating (not shown) can be applied to layer 13 before that the resin layer 14 is applied. The molten resin is allowed to cool and the upper layer 15 is applied thereto (with or without a release coating as mentioned above).

Les films de support 13 et 15 servent à plusieurs usages pratiques dans la présente invention. En premier lieu, en utilisant deux couches, la matière 12 en feuille peut être enroulée ou déroulée aisément de la bobine 10. A ce moment il faut mentionner aussi que si la couche 14 est suffisamment exempte de collant à froid, la couche inférieure 13 peut être éliminée. La deuxième raison pour laquelle un support pour la couche de résine 14 est préféré, est que beaucoup de résines durcissables par un faisceau d'électrons ou un rayonnement ultraviolet sont sensibles à l'exposition à l'air, aussi bien pendant l'entreposage que en particulier pendant le procédé de durcissement. Si la couche 14 est sensible à l'exposition lors de l'entreposage, il faut utiliser à la fois les deux couches 13 et 15. Si la sensibilité apparaît principalement pendant le durcissement, la couche de support inférieure 13 peut être éliminée. L'adhérence entre les films de support et la couche 14 devrait être suffisante pour permettre la manipulation et l'entreposage adéquats du sandwich de résine mais ne devrait pas être aussi grande que pour causer des dommages physiques à la couche 14 lorsque les films de support sont enlevés de celles-ci.The carrier films 13 and 15 serve several practical uses in the present invention. Firstly, by using two layers, the sheet material 12 can be rolled up or unwound easily from the reel 10. At this point it should also be mentioned that if the layer 14 is sufficiently free of cold tack, the lower layer 13 can be eliminated. The second reason why a support for the resin layer 14 is preferred is that many resins curable by an electron beam or ultraviolet radiation are sensitive to exposure to air, both during storage and especially during the curing process. If layer 14 is sensitive to exposure during storage, both layers 13 and 15 should be used at the same time. If the sensitivity occurs mainly during curing, the lower support layer 13 can be removed. The adhesion between the carrier films and layer 14 should be sufficient to allow proper handling and storage of the resin sandwich but should not be as great as to cause physical damage to layer 14 when the carrier films are removed from them.

Le premier stade dans le procédé de l'invention consiste à enlever la couche 13 de la matière 12 en feuille, ce qui est effectué à la figure 1 en utilisant le rouleau récepteur 17. Un rouleau libre 18 est disposé à proximité de la bobine 10 et la couche 13 passe autour de celui-ci et vers le rouleau 17.The first stage in the process of the invention consists in removing the layer 13 from the sheet material 12, which is carried out in FIG. 1 using the take-up roller 17. A free roll 18 is placed near the reel 10 and the layer 13 passes around it and towards the roller 17.

Un autre rouleau d'alimentation 20 contient un rouleau d'acier 22, qui est à revêtir par le procédé de la présente invention. Une paire de rouleaux libres 23 est localisée à proximité mais espacée du rouleau 18, la couche inférieure 13 étant ainsi, en fait, remplacée par l'acier 22 en tant que partie d'un sandwich 25 qui existe en aval des rouleaux 18 et 23.Another feed roller 20 contains a steel roller 22, which is to be coated by the process of the present invention. A pair of free rollers 23 is located near but spaced from the roller 18, the lower layer 13 thus being, in fact, replaced by the steel 22 as part of a sandwich 25 which exists downstream of the rollers 18 and 23 .

Une surface de travail 30 est représentée à la figure 1, laquelle peut prendre n'importe quelle forme appropriée connue dans la technique de revêtement, telle que des rouleaux de transport parallèles et espacés ou une table de travail lisse. Etant donné que la surface de support elle-même ne fait pas partie de la présente invention, des détails de celle-ci ont été omis dans les figures.A work surface 30 is shown in Figure 1, which can take any suitable shape known in the coating art, such as spaced parallel transport rollers or a smooth work table. Since the support surface itself is not part of the present invention, details thereof have been omitted in the figures.

Le stade suivant dans le procédé de l'invention est de former un joint initial entre la couche de résine 14 et l'acier 22. Dans la forme de réalisation illustrée, ceci est effectué en faisant passer les couches 14 et 15 et l'acier 22 par la chambre chauffante 26 où les composants sont chauffés au-dessus de la température de fusion de la couche 14 pour ramollir celle-ci. Dans les dessins, la chambre 26 est représentée comme renfermant une pluralité d'éléments de chauffage 36 disposés au-dessus et au-dessous des feuilles. Les éléments 36 peuvent être des radiateurs du type à résistance, des lampes infrarouges, etc. En outre, on comprendra aisément que les dessins sont en général sous une forme schématique et ne sont pas destinés à limiter la présente invention. D'autres techniques de chauffage peuvent être utilisées, comme par exemple l'usage de rouleaux chauffés touchant une ou les deux feuilles.The next step in the process of the invention is to form an initial seal between the resin layer 14 and the steel 22. In the illustrated embodiment, this is done by passing the layers 14 and 15 and the steel 22 by the heating chamber 26 where the components are heated above the melting temperature of the layer 14 to soften the latter. In the drawings, the chamber 26 is shown as containing a plurality of heating elements 36 disposed above and below the sheets. The elements 36 can be resistance type radiators, infrared lamps, etc. Furthermore, it will be readily understood that the drawings are generally in schematic form and are not intended to limit the present invention. Other heating techniques can be used, such as for example the use of heated rollers touching one or both sheets.

Après le chauffage des matériaux jusqu'à ce que la couche 14 se trouve dans une condition semi-fondue, on fait adhérer la couche 14 à l'acier 22, par exemple en faisant passer l'ensemble entre une paire de rouleaux presseurs 40. A ce stade du procédé, un nouveau sandwich 41 à trois composants est formé.After the materials have been heated until the layer 14 is in a semi-molten condition, the layer 14 is made to adhere to the steel 22, for example by passing the assembly between a pair of pressure rollers 40. At this stage of the process, a new three-component sandwich 41 is formed.

Avant de continuer la description des stades ultérieurs du procédé, il convient de discuter maintenant différentes variantes de la présente invention. Ainsi par exemple, de nombreux matériaux peuvent être substitués au rouleau d'acier 22. Parmi ceux-ci, on peut mentionner d'autres métaux, du papier, du tissu, des films synthétiques, etc. En outre le matériau en rouleau à revêtir, peut être muni d'un primer ou comporter un film d'un enduit d'accrochage (non représenté), si on le désire pour améliorer l'adhérence entre la couche 14 et le matériau en rouleau 22. L'homme de métier, après avoir lu la présente description et après avoir apprécié les principes de base de la présente invention, sera capable de choisir des primers ou des enduits d'accrochage appropriés. Comme exemples de primers ou de couches d'accrochage appropriés, on peut mentionner des esters époxy, des composés époxy durcis par des aminoplastes et/ou des résines époxy durcies par des polyamides ou des amines.Before continuing the description of the subsequent stages of the process, it is now necessary to discuss various variants of the present invention. Thus, for example, many materials can be substituted for the steel roll 22. Among these, mention may be made of other metals, paper, fabric, synthetic films, etc. In addition, the roll material to be coated, can be provided with a primer or include a film of a bonding coating (not shown), if desired to improve the adhesion between layer 14 and the roll material. 22. A person skilled in the art, after having read the present description and after having appreciated the basic principles of the present invention, will be able to choose suitable primers or tack coatings. As examples of suitable primers or bonding layers, there may be mentioned epoxy esters, epoxy compounds cured by aminoplasts and / or epoxy resins cured by polyamides or amines.

Après les stades exposés jusqu'à présent, un sandwich de résine a été préparé, mais la couche de résine 14 est encore à l'état non durci. Pour effectuer le durcissement désiré de ce matériau, le sandwich est exposé à un faisceau d'électrons ou à un rayonnement ultraviolet actinique dans la chambre 42. L'exposition se fait à travers la couche supérieure 15, la couche 14 étant ainsi protégée de l'exposition à l'air pendant le stade de durcissement. Une variété d'appareils est disponible dans le commerce pour effectuer le durcissement par un faisceau d'électrons ou par un rayonnement ultraviolet de matières en feuille, mais des appareils préférés pour l'utilisation dans la mise en oeuvre de la présente invention sont les unités du durcissement par irradiation ultraviolette équipées de lampes à vapeur de mercure, telles que le modèle 18H fabriqué par Ashdee Corp. ou des accélérateurs d'électrons à cathode linéaire ou à balayage tels que ceux fabriqués par Energy Sciences Inc. ou Radiation Polymer Corp. Il convient aussi de rappeler que le procédé illustré à la figure 1 est un procédé continu et que les feuilles se déplacent de manière continue de droite à gauche dans les dessins. Pour cette raison, l'appareil de durcissement doit être capable d'effectuer un durcissement complet de la couche 14 pendant son passage par la chambre 42. Par conséquent, la dimension de la chambre 42 et le nombre d'appareils producteurs de rayonnements qu'elle renferme seront choisis en fonction de la vitesse des feuilles en mouvement, de la résine particulière utilisée dans la couche 14 et de l'épaisseur de la couche 14. La vitesse de durcissement peut également dépendre du colorant ou de la pigmentation de la couche 14, des facteurs qui seront aisément appréciés pour l'homme du métier après la lecture de la présente description. A titre d'exemple et en utilisant l'appareil de durcissement Ashdee cité ci-dessus, un durcissement complet d'une résine "hot melt" uréthane-acrylate peut être effectué en une épaisseur de 127, 381 ou 762 Ym à une vitesse de 15,24 m/mn. Dans cet exemple, la couche supérieure 15 est du poly(téréphtalate d'éthylène) de 127 rm et le matériau en rouleau 22 est de la tôle d'acier munie d'un primer de copolymère acétate de vinyle-chlorure de vinyle.After the stages described so far, a resin sandwich has been prepared, but the resin layer 14 is still in the uncured state. To effect the desired hardening of this material, the sandwich is exposed to an electron beam or to actinic ultraviolet radiation in chamber 42. The exposure takes place through the upper layer 15, the layer 14 being thus protected from the exposure to air during the curing stage. A variety of apparatuses are commercially available for effecting curing by an electron beam or by ultraviolet radiation of sheet materials, but preferred apparatuses for use in the practice of the present invention are the units curing by ultraviolet irradiation equipped with mercury vapor lamps, such as the 18H model manufactured by Ashdee Corp. or linear or scanning cathode electron accelerators such as those manufactured by Energy Sciences Inc. or Radiation Polymer Corp. It should also be remembered that the process illustrated in Figure 1 is a continuous process and that the sheets move continuously from right to left in the drawings. For this reason, the curing apparatus must be capable of effecting a complete curing of the layer 14 during its passage through the chamber 42. Consequently, the dimension of the chamber 42 and the number of radiation producing apparatuses that it contains will be chosen according to the speed of the moving sheets, the particular resin used in layer 14 and the thickness of layer 14. The hardening speed may also depend on the dye or pigmentation of layer 14 , factors which will be readily appreciated by those skilled in the art after reading this description. By way of example and using the Ashdee curing apparatus cited above, a complete curing of a urethane-acrylate "hot melt" resin can be carried out in a thickness of 127, 381 or 762 Y m at a speed 15.24 m / min. In this example, the upper layer 15 is poly (ethylene terephthalate) of 127 rm and the roll material 22 is sheet steel provided with a primer of vinyl acetate-vinyl chloride copolymer.

Une fois que la couche 14 a été durcie à l'état solide, le stade final du procédé de la présente invention comprend l'enlèvement de la feuille supérieure 15. Ceci est effectué en tirant la feuille autour d'un autre rouleau libre 43 et en enroulant la feuille supérieure 15 autour de la bobine réceptrice 44. Les feuilles de support peuvent être mises au rebut, réutilisées dans le procédé ou encore recyclées.Once layer 14 has been solidified, the final stage of the process of the present invention comprises removing the top sheet 15. This is done by pulling the sheet around another free roll 43 and winding the top sheet 15 around the take-up reel 44. The carrier sheets can be discarded, reused in the process or recycled.

La présente invention fournit un substrat enduit avec une adhérence entre le revêtement et le substrat qui est plus grande que celle obtenue en appliquant des revêtements de types similaires à l'état liquide et en utilisant un durcissement par un faisceau d'électrons ou par un rayonnement ultraviolet. A titre d'exemple, l'adhérence de l'article enduit confectionné dans l'exemple cité ci-dessus était de 100% par la méthode d'essai sur entailles en croix et décollage d'un ruban ("cross hatch and tape pull method" en anglais) comparé à une adhérence de 0 à 25% en utilisant la même méthode d'essai lorsqu'un article enduit était préparé en appliquant un film liquide d'une résine d'un ester vinylique comme revendiqué dans le brevet américain 4.216.306,en une épaisseur de 127, 381 ou 762 rm sur de l'acier muni d'un primer similaire avec un durcissement effectué par un appareil de durcissement Ashdee et une vitesse de défilement de 15,24 m/mn.The present invention provides a coated substrate with an adhesion between the coating and the substrate which is greater than that obtained by applying coatings of similar types in the liquid state and using curing by an electron beam or by radiation. ultraviolet. By way of example, the adhesion of the coated article made up in the example cited above was 100% by the test method on cross cuts and peeling of a ribbon ("cross hatch and tape pull method "compared to 0-25% adhesion using the same test method when a coated article was prepared by applying a liquid film of a vinyl ester resin as claimed in US Patent 4,216 .306, in a thickness of 127, 381 or 762 rm on steel provided with a similar primer with hardening carried out by an Ashdee hardening apparatus and a running speed of 15.24 m / min.

La description précédente de la forme de réalisation préférée de la présente invention est donnée à titre d'illustration plutôt que de limitation. Une modification serait d'utiliser une couche de résine 14 supportée sur la face supérieure comme représentée à la figure 3. Le procédé est identique à celui de la figure 1, sauf que le rouleau libre 18 et le rouleau récepteur 17 sont éliminés. En outre, dans la figure 3, une couche de primer 45 est représentée comme étant appliquée sur le matériau 22 avant son passage par les rouleaux 23. Le sandwich formé dans cette forme de réalisation est représenté à la figure 4 au-dessus de la table de travail 30. Une autre modification est représentée à la figure 5 dans laquelle la couche 14 est pigmentée en 46 de manière décorative avant l'application au matériau en rouleau 22. De plus, comme mentionné plus haut, la couche de résine 14 servant de revêtement peut être colorée, pigmentée ou encore gaufrée selon n'importe quel motif souhaité. Il faut aussi mentionner que bien que le procédé soit illustré comme étant continu et comportant l'usage de matériaux en rouleau, les mêmes principes sont applicables au même titre au revêtement de matériaux en forme de feuille avec des feuilles de résine solide non durcie. Ainsi, bien que la présente invention a été décrite en relation avec,la forme de réalisation préférée et les deux modifications illustrées, elle n'est pas limitée aux modes illustrés mais elle est seulement limitée par les revendications qui suivent.The foregoing description of the preferred embodiment of the present invention is given by way of illustration rather than limitation. A modification would be to use a resin layer 14 supported on the upper face as shown in FIG. 3. The process is identical to that of FIG. 1, except that the free roller 18 and the take-up roller 17 are eliminated. Furthermore, in FIG. 3, a layer of primer 45 is shown as being applied to the material 22 before it passes through the rollers 23. The sandwich formed in this embodiment is shown in FIG. 4 above the table working 30. Another modification is shown in FIG. 5 in which the layer 14 is pigmented at 46 in a decorative manner before the application to the roll material 22. In addition, as mentioned above, the resin layer 14 serving as coating can be colored, pigmented or embossed in any desired pattern. It should also be mentioned that although the process is illustrated as being continuous and involving the use of roll materials, the same principles are equally applicable to the coating of materials sheet-shaped with sheets of uncured solid resin. Thus, although the present invention has been described in connection with, the preferred embodiment and the two illustrated modifications, it is not limited to the illustrated modes but it is only limited by the claims which follow.

Claims (6)

1. Procédé pour appliquer sur un substrat un revêtement de résine durcie par un faisceau d'électrons ou par un rayonnement ultraviolet, caractérisé en ce que (1) on applique sur le substrat à revêtir un film de revêtement d'une résine non durcie qui fond à une température élevée et qui est solide à des températures inférieures à environ 10-32°C, la résine étant choisie parmi les résines durcissables par exposition à un faisceau d'électrons et les résines durcissables par exposition à un rayonnement ultraviolet; (2) on fait adhérer le film de revêtement au substrat tout en maintenant la résine à l'état non durci; et, (3) on durcit ensuite le film de revêtement par exposition à un faisceau d'électrons ou à un rayonnement ultraviolet. 1. Method for applying a coating of resin hardened by an electron beam or by ultraviolet radiation on a substrate, characterized in that (1) a coating film of an uncured resin which melts at an elevated temperature and which is solid at temperatures below about 10-32 ° C is applied to the substrate to be coated, the resin being chosen from curable resins by exposure to an electron beam and the curable resins by exposure to ultraviolet radiation; (2) the coating film is adhered to the substrate while maintaining the resin in the uncured state; and, (3) the coating film is then cured by exposure to an electron beam or to ultraviolet radiation. 2. Procédé selon la revendication 1, caractérisé en ce que le substrat est choisi parmi des métaux, un papier, un tissu et des films synthétiques.2. Method according to claim 1, characterized in that the substrate is chosen from metals, paper, fabric and synthetic films. 3. Procédé selon les revendications 1 ou 2, caractérisé en ce que le film de revêtement comporte sur ses deux faces et avant le stade d 'adhésion, une feuille de support détachable de résine synthétique, en ce qu'une des deux feuilles de support est enlevée avant le stade d'adhésion pour que le film de revêtement puisse être collé au substrat et en ce que l'autre feuille de support est enlevée du film de revêtement après le stade de durcissement.3. Method according to claims 1 or 2, characterized in that the coating film comprises on its two faces and before the stage of adhesion, a detachable support sheet of synthetic resin, in that one of the two support sheets is removed before the adhesion stage so that the coating film can be bonded to the substrate and in that the other support sheet is removed from the coating film after the curing stage. 4. Procédé selon les revendications 1 ou 2, caractérisé en ce que le film de revêtement comporte sur une face une feuille de support détachable de résine synthétique et en ce que l'autre face est collée sur le substrat pendant le stade d'adhésion, la feuille de support étant enlevée du film de revêtement après le stade de durcissement.4. Method according to claims 1 or 2, characterized in that the coating film comprises on one side a detachable support sheet of synthetic resin and in that the other side is bonded to the substrate during the adhesion stage, the backing sheet being removed from the coating film after the curing stage. 5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le substrat est muni d'un primer ou d'un enduit d'accrochage.5. Method according to any one of claims 1 to 4, characterized in that the substrate is provided with a primer or a bonding coating. 6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le stade d'adhésion comprend le chauffage de la résine au-dessus de son point de fusion pour la ramollir, l'application d'une pression conjointement sur le film de revêtement et sur le substrat et le refroidissement de la résine afin de la solidifier avant le stade de durcissement.6. Method according to any one of claims 1 to 5, characterized in that the adhesion stage comprises the heating of the resin au- above its melting point to soften it, applying pressure jointly to the coating film and the substrate and cooling the resin to solidify it before the curing stage.
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