EP3122475B1 - Procédé pour peindre des substrats plats présentant une haute perfection de surface avec une polymérisation radicalaire induite par lampes à del, et éléments peints au moyen de ce procédé - Google Patents

Procédé pour peindre des substrats plats présentant une haute perfection de surface avec une polymérisation radicalaire induite par lampes à del, et éléments peints au moyen de ce procédé Download PDF

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Publication number
EP3122475B1
EP3122475B1 EP15713375.2A EP15713375A EP3122475B1 EP 3122475 B1 EP3122475 B1 EP 3122475B1 EP 15713375 A EP15713375 A EP 15713375A EP 3122475 B1 EP3122475 B1 EP 3122475B1
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Prior art keywords
painting
paint
plastic
flat
painted
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EP15713375.2A
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German (de)
English (en)
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EP3122475A1 (fr
Inventor
Luca Sparapani
Fabio PANICCIA
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ICA SpA
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ICA SpA
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    • 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
    • B05D1/40—Distributing applied liquids or other fluent materials by members moving relatively to surface
    • B05D1/42—Distributing applied liquids or other fluent materials by members moving relatively to surface by non-rotary members
    • 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
    • B05D3/0218—Pretreatment, e.g. heating the substrate
    • 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
    • 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
    • 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
    • B05D2201/00—Polymeric substrate or laminate
    • B05D2201/02—Polymeric substrate
    • 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
    • B05D2201/00—Polymeric substrate or laminate
    • B05D2201/04—Laminate
    • 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
    • B05D2203/00—Other substrates
    • B05D2203/20—Wood or similar material
    • 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
    • B05D2252/00—Sheets
    • B05D2252/02—Sheets of indefinite length

Definitions

  • the present invention concerns a process for finishing substrates made of plastic, laminated or wooden material, in particular polymethylmethacrylate (PMMA), between 10 micron and 1 cm thick, using paints with radical cross-linking induced by LED sources with wavelengths between 320 and 450 nm, and the elements obtained with this process.
  • PMMA polymethylmethacrylate
  • PMMA is a plastic material that has excellent mechanical and optical properties, such as excellent light stability and an intrinsic low resistance to chemical agents. But PMMA is not scratch resistant, although it has better resistance than other plastics.
  • paints that will improve their surface hardness, chemical resistance, surface cleanliness, slipperiness and scratch-proof properties, provided that they are applied in such a way as to ensure their good adhesion to the painted substrate, their good level of polymerization and their high surface hardness.
  • UV paints with radical cross-linking induced by UV radiation are known (hereinafter called UV paints), characterized by rapid polymerization (milliseconds), high surface hardness and high degrees of cross-linking.
  • UV paints can be diluted with water, with solvent or be without either. These last, hereinafter called 100% UV paints, are the most suitable because, since they are without solvents and water, they have rapid polymerization times and other advantages such as higher hardness, higher scratch resistance and low degree of yellowing on exposure to natural elements.
  • UV paints are generally mixtures of copolymers containing unsaturated bonds and the presence of one or more acrylic or polyester groups with acrylic monomers and photoinitiators. Moreover, these paints can be mixed with silicone substances, polysiloxanes, waxes or other substances to improve some properties such as slipperiness, spreading, wetting of the substrate, adhesion or other surface characteristics.
  • Solvent-based UV paints are generally made as above, but solvent is added to aid their spreading, ease of application and adhesion to the substrate, if it is necessary to improve these characteristics compared to 100% UV paints.
  • water-based UV paints are characterized by the use of water-thinnable copolymers, or by dispersions or aqueous emulsions of acrylic, polyurethane, urethane acrylate or polyester oligomers.
  • UV paint can be applied by spraying, by curtain coating, or by roller; the most suitable method is, however, by roller, due to its high speeds (up to 30 m/min) and also because it requires low quantities of paint (5-10 micron of paint) to be evenly applied over the entire surface to be painted, without using solvents and, above all, with a near 100% coefficient of transfer.
  • UV paint by roller The problem with applying UV paint by roller is that a good spread of it over the painted surface is not obtained, so nullifying its aesthetic result and therefore altering the visual perception that can be obtained with PMMA.
  • the release is generally made of polyester (known by the commercial name of Mylar®, Melinex®, Lumirrot®, Terphane®, Hostaphane®), polypropylene, nylon, PET, PVF, CPP, silicone or any other thin (less than 1 cm) plastic material that is optically transparent or semi-transparent and with high transmittance at wavelengths below 380 nm.
  • polyester known by the commercial name of Mylar®, Melinex®, Lumirrot®, Terphane®, Hostaphane®
  • polypropylene nylon
  • PET PET
  • PVF polypropylene
  • CPP silicone or any other thin (less than 1 cm) plastic material that is optically transparent or semi-transparent and with high transmittance at wavelengths below 380 nm.
  • the process of UV painting and treatment with release is generally called embossing.
  • This process is currently used for the treatment of numerous flat surfaces, including wood - as per teaching of patent US20040094262A1 ; wood fibre as per teaching of patent EP2271492A2 ; laminates as per teaching of patent US6423167B1 ; glass, plastic.
  • the treatment can give the surface to be painted a smooth or textured appearance, as per teaching of patent DE202004018710U1 , so as to be able to control its gloss; or particular optical structures as per teaching of patent US20110011390A1 .
  • UV paint is currently polymerized through the use of gallium or mercury doped UV lamps with powers between 80 W/cm and 200 W/cm. These lamps have variable emission, as shown in the graph of Fig. 1 .
  • mercury lamps have an emission maximum at 320 and 360 nm and gallium lamps at 360 and 420 nm.
  • Patent US20100258051A1 describes and claims an embossing process in which UV paint is applied by roller; the release is applied immediately after the paint has been spread on, and the painted substrate, coupled with the release, is passed under one or more UV lamps to start the polymerization process. After passing under the UV lamp, the release is removed and then recovered.
  • UV lamps pose numerous problems also connected with the optical properties of the release.
  • the first problem arises from the use of releases that are not completely transparent to UV radiation; in particular, there can be transmittance values below 5% for wavelengths below 320 nm.
  • UV lamps emit their energy only partially in the form of UV radiation, while most of the energy is emitted as visible light and high heat on the surface to be polymerized generated by parabolas.
  • the high heat is a problem in the process of painting plastic because it softens it, changes its surface structure and releases molecules that are not perfectly polymerized (elasticizers, phthalates, monomers, etc.) that can affect the paint polymerization process and the final properties of the paint.
  • UV radiation is generally an electromagnetic radiation between 4 and 380 nm ( The American Heritage Dictionary of the English Language, Fourth Editi on ).
  • LED lamps which can emit a monochromatic source of light at a specific wavelength.
  • LED lamps can have powers between 2 and 20 W/cm and wavelengths between 300 and 420 nm.
  • These LED lamp wavelengths absorb photoinitiators such as acylphosphine oxides (BAPO, MAPO, TPO-L). This type of photoinitiator is widely used for making pigmented or thickly applied UV paints.
  • the use of a release, as well as improving the spreading of the UV paint, also has an inactivating function on the surface of the painted substrate.
  • the quantity of oxygen on the painted substrate is very low. This allows the problem of inhibition of the oxygen typically present in the polymerization of UV paints with LED lamps, due to the absence of UV radiation below 300 nm, to be overcome.
  • the release is removed from the surface of the painted substrate and is recovered.
  • the process of heating the surface of the substrate to be painted is particularly suitable if it is made of plastic because it aids its process of adhesion to the paint.
  • the PMMA substrate between 10 micron and 1 cm thick, to be painted, it is necessary to pre-heat it to a temperature between 40 and 70°C at the time of contact with the paint. Lower temperatures can cause problems of adhesion of the paint on the PMMA substrate to be painted.
  • the temperature also aids the mechanism of spreading of the paint over the PMMA substrate to be painted. Heating can be carried out for example with IR, NIR, UV lamps, heating elements or any other equipment suitable for transferring energy in the form of heat.
  • monochromatic LED lamps also provides undoubted advantages on the life of the release used.
  • the radiation generated by a conventional UV lamp covers a wide spectrum of frequencies that range from UV to IR; this can trigger degradation mechanisms on the material used for the release that, over time, can change some chemical and physical properties (elasticity, transparency, etc.). This problem is even more evident with re-usable releases, or with continuous silicone releases. In particular, in continuous silicone releases, it is possible to observe a rapid decline in transparency due to the use of gallium UV lamps that trigger secondary mechanisms of degradation of the belt.
  • LED lamps for the polymerization of paints has been known for some time (for example, US 20130224495 A1 , US 8569393 B2 ) as also has the use of acylphosphine oxide based photoinitiators for their polymerization (for example, EP2448427A ).
  • inert atmospheres for the polymerization of UV paints is also a known process, but the most commonly used method is to use inert gases to remove oxygen from the surface of the paint to be polymerized (for example, US 8567936 B2 ).
  • LED lamps or sources with wavelengths above 320 nm therefore allows this problem to be overcome, by providing higher powers (expressed as W/cm 2 ) than conventional arc lamps, with all the above-described benefits in terms of release life, lower generation of heat and a better degree of polymerization of the UV paint used.
  • PMMA polymethylmethacrylate
  • PMMA polymethylmethacrylate
  • PMMA polymethylmethacrylate
  • the present invention concerns a process for painting on the flat of substrates made of plastic material, in particular polymethylmethacrylate (PMMA), between 10 micron and 1 cm thick, or of laminated or wooden material, having a different conveying system depending on whether the substrate to be painted is continuous or non-continuous.
  • PMMA polymethylmethacrylate
  • a continuous or non-continuous release and a conveyor belt (1) that coincides with the reel itself are used; whereas when the substrate to be painted is non-continuous (plastic slabs, wood or laminated panels), a non-continuous or continuous release and the conveyor belt shown in Fig. 4 with (1) and (12) are used.
  • the release is considered continuous when both element (9) and element (13) are present; it is considered non-continuous when element (9) is present and element (13) is absent.
  • the conveying system consists of a conveyor belt (1) whose function is to bring the substrate into contact with the painting elements and the equipment connected with it, such as for example, the painting roller and the release.
  • conveyor belt (12) is present and is a continuous system with conveyor belt (1).
  • the conveyor belt (12) is not necessary, but it is necessary to use an unwinding (10) and winding (11) mechanism so as to move the substrate to be painted and keep it at the right tension to obtain an even painting of it and correct coupling of the release on the surface.
  • the conveyor belt (12) can in any case be present, since it does not hinder the painting process.
  • the conveying system In the case of reels, the conveying system consists of a reel unwinding mechanism (10) and a reel winding mechanism (11). The speed of the winding and unwinding mechanisms must be identical; the speed of these elements determines the speed of the conveying system. In this case too, the conveying system is used to bring the substrate into contact with the painting elements and the equipment connected with it, such as for example, the painting roller and the release.
  • the conveying system for continuous or non-continuous substrates is at variable speed between 1 and 30 m/min.
  • the process for painting substrates made of plastic material, in particular polymethylmethacrylate (PMMA), between 10 micron and 1 cm thick, or of laminated or wooden material, that is the subject of the present invention is characterized in that it uses paints with radical cross-linking induced by one or more LED sources (6) with wavelengths between 320 and 450 nm with a variable power between 2 and 20 W/cm and this LED source (6) is placed at a height from the substrate to be painted of between 0.1 mm and 10 cm behind the release.
  • PMMA polymethylmethacrylate
  • the surface of the flat substrate to be painted is cleaned of any residues with ionizing radiations or other cleaning systems; then the surface of the flat substrate is heated by heating elements, IR lamps, NIR lamps, or the use of plasma ionization technologies, corona treatment, and a combination of these to aid adhesion of the paint to the substrate to be painted.
  • the substrate to be painted can alternatively also consist of wooden, plastic or cellulosic material, glass or combinations with each other.
  • paint is applied on it by a system of application rollers (2) and (3) each having a doctor roller (2a) (3a) with independent speed for regulating the quantity of paint to be applied.
  • the application rollers (2) and (3) are coated with rubber or silicone or polyurethane or alternatively have a smooth surface engraved with regular structures (lines, dots or patterns).
  • the system of application rollers (2) and (3), as described above and shown in Fig. 4 can be replaced by other paint application systems such as for example curtain coating, spray, offset , flexo or slot-die systems, mentioned only as alternatives but not described and not shown in the present application.
  • the quantity of paint to be applied on the flat substrate up to roller (5) can range between 2 and 100 micron.
  • the function of roller (5) is also to couple the continuous painted flat substrate with the continuous or non-continuous release of known thickness or the non-continuous painted flat substrate with the non-continuous or continuous release of known thickness, on which the paint is evenly distributed for the distance between the coupling roller (5) and its recovery roller (8); moreover, one or more LED lamps or sources (6) for polymerization of the paint are positioned between the coupling roller (5) and the recovery roller (8). If the release is continuous, its movement is brought about by a system of upper winders (4) and (7) connected with the lower coupling roller (5) and recovery roller (8), as illustrated in Fig. 4a .
  • the painted flat substrate is ready to be protected with a peelable paint or with a protective coating of plastic material, or rewound by the winding mechanism (11).
  • the UV paint used can be free of volatile substances (100% paint) or contain water (water-based paint), or contain solvents (solvent-based paint).
  • the UV paint is a mixture of oligomeric polymers, monomers, photoinitiators, additives, mineral fillers, pigments and dyes with a solid content above 30%.
  • the 100% UV paint is a mixture of oligomeric polymers, monomers, photoinitiators, additives, mineral fillers, pigments and dyes with a solid content above 30% and containing water or solvents.
  • UV paint An example of formulation of a UV paint is the following: Raw material % by weight Aliphatic urethane acrylate oligomer 40-50% Acrylic monomer 30-50% Adhesion promoting additive 0.5-5% Photoinitiator 1-5% Additives 0.1-2%
  • An example of formulation for a solvent-based UV paint is the following: Raw material % by weight Aliphatic urethane acrylate oligomer 80-20 % Acrylic monomer 10-70 % Solvent 5-70 % Photoinitiator 1-5 % Additives 0.1-2%
  • An example of formulation for a water-based UV paint is the following: Raw material % by weight Water-based UV oligomer (dispersion, emulsion, solution) 20-80 % Water 10-70 % Additives 0.1-5% Photo initiator 1-5 %
  • the indicated formulation is applied by EPDM 40 shore roller with a quantity of 8 g/m 2 .
  • the substrate Prior to application, the substrate is subjected to a corona treatment and the surface is heated to 50°C.
  • the release is applied on the painted surface (Melinex 425) and, after 10 seconds, the paint is polymerized with a LED lamp of 395 nm wavelength with power of 8 W/cm placed at 1 mm from the surface.
  • the solvent must be removed from the film of paint applied on the substrate to be painted before application of the continuous or non-continuous release.
  • This stage can take place by increasing the time, between 10 seconds and 10 minutes, between the stage of applying the paint on the substrate to be painted and the stage of contact with the coupling roller (5) of the release.
  • hot air IR lamps, laminar air flows, catalytic plates, or any other technology suitable for this application, also in combination with each other (14).
  • the solvent content is generally between 10 and 70%.
  • the process described above for products containing solvents must be adopted in the case of UV paints containing water, in which, as an alternative, it is possible to use the above-mentioned example formulation, using, in place of the aliphatic urethane acrylate oligomer, aqueous emulsions or aqueous solutions or aqueous dispersions of acrylic, polyurethane, urethane acrylate or polyester resins, or combinations of these.
  • the water content is between 10 and 70%.
  • Fig. 5 illustrates the variant of the above-described process, in which the painting line has been lengthened and a heating unit (14) having IR lamps, or heating plates, or hot air flows, or catalytic plates or whatever located before the coupling roller (5), has been added.
  • a heating unit (14) having IR lamps, or heating plates, or hot air flows, or catalytic plates or whatever located before the coupling roller (5), has been added.

Claims (8)

  1. Procédé permettant de peindre sur la surface plane de substrats en matière plastique notamment en polyméthacrylate de méthyle (PMMA) -, d'une épaisseur comprise entre 10 microns et 1 cm, ou encore en matériau stratifié ou en bois, qui dispose d'un système de convoyage dont la vitesse varie de 1 à 30 m/min pour les substrats plats utilisant un diffuseur en matière plastique en fonction d'épaisseurs connues, caractérisé en ce qu'il utilise des peintures à réticulation radicalaire induites par une ou plusieurs sources DEL (6) placées à une hauteur, par rapport au substrat à peindre, se situant entre 0,1 mm et 10 cm derrière le diffuseur et dont les longueurs d'onde sont comprises entre 320 et 450 nm, ainsi qu'une puissance variable allant de 2 à 20 W/cm.
  2. Procédé permettant de peindre sur la surface plane de substrats en matière plastique, en matériau stratifié ou en bois selon la revendication 1, caractérisé en ce que le substrat en PMMA à peindre est préalablement traité par des rayonnements ionisants ou d'autres systèmes de nettoyage, mais également par combinaison entre ces systèmes.
  3. Procédé permettant de peindre sur la surface plane de substrats en matière plastique, en matériau stratifié ou en bois selon la revendication 1, caractérisé en ce que le substrat en PMMA à peindre doit être porté à une température se situant entre 40 et 70°C au moment de son contact avec la peinture.
  4. Procédé permettant de peindre sur la surface plane de substrats en matière plastique, en matériau stratifié ou en bois selon la revendication 1, caractérisé en ce que la peinture est appliquée par un ou plusieurs rouleaux, un ou plusieurs pulvérisateurs, une ou plusieurs coucheuses à nappe, une ou plusieurs filières à fente ou par combinaison entre ces systèmes.
  5. Procédé permettant de peindre sur la surface plane de substrats en matière plastique, en matériau stratifié ou en bois selon la revendication 1, caractérisé en ce que la peinture UV est un mélange de polymères oligomères, de monomères, de photo-initiateurs, d'additifs, de charges minérales, de pigments et de colorants, avec une teneur en solides supérieure à 30 %.
  6. Procédé permettant de peindre sur la surface plane de substrats en matière plastique, en matériau stratifié ou en bois selon la revendication 1, caractérisé en ce que la peinture UV est un mélange de polymères oligomères, de monomères, de photo-initiateurs, d'additifs, de charges minérales, de pigments et de colorants, avec une teneur en solides supérieure à 30 % contenant de l'eau ou un solvant.
  7. Procédé permettant de peindre sur la surface plane de substrats en matière plastique, en matériau stratifié ou en bois selon les revendications 1 à 6, caractérisé par une extension de la ligne de peinture et par un corps de chauffe (14) doté de lampes infrarouges, de plaques chauffantes, de flux d'air chaud, de plaques catalytiques ou de tout autre système, situé avant le rouleau de couplage (5) en cas de peintures UV à base d'eau ou de peintures UV à base de solvant.
  8. Procédé permettant de peindre sur la surface plane de substrats en matière plastique, en matériau stratifié ou en bois selon l'une quelconque des revendications précédentes, caractérisé en ce que le substrat à peindre, tout comme il est constitué d'une surface en PMMA, en polycarbonate, en propionate de cellulose ou en acétate de cellulose, peut être constitué par ailleurs d'un matériau en verre, en cellulose, en plastique, en bois ou de ces matériaux combinés.
EP15713375.2A 2014-03-26 2015-03-20 Procédé pour peindre des substrats plats présentant une haute perfection de surface avec une polymérisation radicalaire induite par lampes à del, et éléments peints au moyen de ce procédé Active EP3122475B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITAN20140049 2014-03-26
PCT/EP2015/000620 WO2015144304A1 (fr) 2014-03-26 2015-03-20 Procédé pour peindre des substrats plats présentant une haute perfection de surface avec une polymérisation radicalaire induite par lampes à del, et éléments peints au moyen de ce procédé

Publications (2)

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EP3122475A1 EP3122475A1 (fr) 2017-02-01
EP3122475B1 true EP3122475B1 (fr) 2019-06-12

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EP (1) EP3122475B1 (fr)
ES (1) ES2745437T3 (fr)
WO (1) WO2015144304A1 (fr)

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IT201800010863A1 (it) 2018-12-06 2020-06-06 Ind Chimica Adriatica S P A In Sigla Ica S P A Sistema meccanico di riflessione ed irraggiamento per la reticolazione di vernici polimerizzabili uv.

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ITPS20010006A1 (it) * 2001-02-23 2002-08-23 Canti & Figli Srl Procedimento e macchina atti ad ottenere goffrature su superfici verniciate di pannelli o di pellicole di rivestimento ed elementi ottenuti
EP2814859A4 (fr) * 2012-02-16 2015-07-29 Arkema Inc Composition adhésive durcissable par rayonnement pour feuilles arrière photovoltaïques

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WO2015144304A1 (fr) 2015-10-01
EP3122475A1 (fr) 2017-02-01

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