EP2994242B1 - Spray-coating method - Google Patents

Spray-coating method Download PDF

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Publication number
EP2994242B1
EP2994242B1 EP14725032.8A EP14725032A EP2994242B1 EP 2994242 B1 EP2994242 B1 EP 2994242B1 EP 14725032 A EP14725032 A EP 14725032A EP 2994242 B1 EP2994242 B1 EP 2994242B1
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EP
European Patent Office
Prior art keywords
process according
filler
employed
thermoplastically processable
spraying
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EP14725032.8A
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German (de)
French (fr)
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EP2994242A1 (en
Inventor
Norbert Nicolai
Volkmar Schulze
Thomas Karcz
Sergej Kohlert
Joachim Meyke
Holger Schaarschmidt
Toni Nippe
Christian Urban
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Adler Pelzer Holding GmbH
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Adler Pelzer Holding GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/16—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/24—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas with means, e.g. a container, for supplying liquid or other fluent material to a discharge device
    • B05B7/26—Apparatus in which liquids or other fluent materials from different sources are brought together before entering the discharge device
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/24—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas with means, e.g. a container, for supplying liquid or other fluent material to a discharge device
    • B05B7/26—Apparatus in which liquids or other fluent materials from different sources are brought together before entering the discharge device
    • B05B7/262—Apparatus in which liquids or other fluent materials from different sources are brought together before entering the discharge device a liquid and a gas being brought together before entering the discharge device
    • 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
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying

Definitions

  • the invention relates to a method for spray coating of substrate surfaces, which makes it possible to apply different thermoplastically processable materials on a variety of surfaces by means of spray technology.
  • thermoforming, vacuum thermoforming and pressing for processing films into molded parts or individual layers are known.
  • heavy-layer foils are placed on carpet or end wall areas from the acoustic point of view, where they stick or melt.
  • thermoplastic injection molding or reaction injection molding (RIM)
  • RIM reaction injection molding
  • the tool geometry determines the mass distribution for all abutments. This also prevents the targeted acoustic optimization of individual vehicle types (engine variants) within a series that would be desirable from an acoustic point of view.
  • thermoplastics are known methods for coating as well as the production of planar components by spraying.
  • the spraying of thermoplastics is done either from the melt by means of one or more nozzles or "cold" plastic powder by heating a flame during the flight phase and a carrier gas or directly by a hot environment during the flight phase.
  • these methods have very low throughputs and are conditionally suitable for coating temperature-resistant substrates.
  • the high temperatures would destroy the fabric before it has been applied.
  • the spray process is also used in powder regeneration.
  • DE 10 2005 050 890 A1 describes a method and apparatus for producing a nanocomposite, in which the separation of extraction and optionally dispersing agent from a polymer melt by the high-pressure spraying process takes place. This solidify the polymer droplets abruptly due to the taking place during the relaxation of the high pressure level to ambient pressure strong cooling. This produces the nanocomposites.
  • a plastic strand is deposited on a mostly pretreated substrate surface.
  • EP 0 524 092 B2 For example, a method and apparatus for making an article having a molded tread is described.
  • the profile strand is produced and deposited by an extrusion head which is connected to the extruder via a heated flexible pressure hose.
  • DE 30 47 727 C2 describes a process for producing thin protective films by spraying liquefied thermoplastic material.
  • the method described here is intended to enable the use of conventional hot spraying equipment, in which spray material is melted and thus liquefied, which can then be applied directly to the protective surface. It is further described that the tendency of these materials to form beads after hitting the surface has not heretofore yielded a sufficiently homogeneous film, but according to this description, it is most convenient to address them by a simultaneous or subsequent sintering operation.
  • the sintering of the thermoplastic material it has accordingly been found to be advantageous if the sintering is carried out by heating the sprayed-on thermoplastic material so as to obtain a uniform, smooth and nonporous application.
  • the heat required for sintering can be supplied to the thermoplastic material from the outside by heat radiation, hot air supply or the like. It may be useful, the thermoplastic material to a previously to spray heated surface, so that the sintering process is carried out simultaneously with a spraying and thus a temporally optimal process flow is obtained. However, the sintering process carried out after the impact of the material on the surface is very complicated and thermally re-stresses the substrate material.
  • DT 16 46 051 B2 describes a process for applying polymeric coatings to solid surfaces by spraying a molten thermoplastic polymer. Thereafter, the melting of the polymer and the supply of the melt in a compressed gas stream is carried out by the injection pressure method and subjected to the sprayed gas / polymer beam during its path to the surface to be coated, a heat radiation treatment. It is described to convert the thermoplastic polymer of any particle size in extruders or piston-cylinder devices in the molten state and sprayed by means of compressed air by means of a compressed air injection nozzle in the form of a heated by a heat flow gas / polymer jet on the surface to be coated, which previously heated becomes.
  • DE 32 25 844 A1 describes a method and apparatus for applying layers of thermoplastic or hot melt adhesives.
  • a method is described for applying layers of thermoplastic materials or hot-melt adhesives, in which the plastic or hot-melt adhesive used is melted, then atomized and sprayed.
  • the temperature of the molten plastic or hot melt adhesive is kept constant until the moment of spraying.
  • the device for carrying out the Method includes a heatable melting device for a plastic or hot melt adhesive, a nozzle having a heated spray device, a heatable feeder of the molten material in the spray device, a temperature measuring and temperature control system and control systems for the supply and delivery of a molten material and possibly the heated spray gas ,
  • a heatable melting device for a plastic or hot melt adhesive for a plastic or hot melt adhesive
  • a nozzle having a heated spray device a heatable feeder of the molten material in the spray device
  • a temperature measuring and temperature control system and control systems for the supply and delivery of a molten material and possibly the heated spray gas
  • DE 42 31 074 A1 describes the use of plastic powders as filler in sprayable and sprayable coating materials, paints and sealants. Described is the use of powders of the density range 0.1 to 2.0 g / cm 3 of a mean particle size of not more than 0.2 mm, which have been obtained by mechanical comminution of optionally mineral fillers, solid plastics, as a filler, optionally in addition other fillers in sprayable and sprayable paints, coating and sealing compounds based on one- or two-component polyurethane binders.
  • DE 101 61 600 A1 describes a method for spraying plastic layers.
  • a method and apparatus for applying a filler-containing plastic layer to a shaped surface wherein a mixture containing binder mixture, solids promoter and filler is sprayed onto the shaped surface by first blasting a mixture containing binder mixture and solids promoter to the Spray application produced and then added the filler in the free jet of not yet polymerized binder mixture.
  • the method is particularly suitable for the spray application of heavy layers, as sin are used in conventional mass-spring systems.
  • DE 10 2005 058 292 A1 describes a method and an apparatus for producing coated moldings.
  • a method and an apparatus for producing molded parts comprising a layer of polyurethane in the weft operation, in which the reactive components are mixed with a cylindrical mixing chamber and the reactive mixture produced then flows through a flow channel and is sprayed onto the surfaces of a substrate and cured and then the flow channel is cleaned by a gas stream.
  • US 5,605,720 A describes a continuous in-line process for preparing and applying hot melt adhesives to a substrate by dosing a polymer adhesive and a tackifier in a particular weight ratio in an extruder in which these raw materials form a homogeneous melt.
  • the melt is continuously added directly to a hot melt applicator and applied to a substrate.
  • CH 497 291 A relates to methods for applying coatings of polymeric materials to the surface of products by spraying, in which the polymer is heated to a temperature which is higher than its melting point, and the melt obtained by means of compressed gas to be coated on the Produced surface is sprayed, wherein the jet flowing out of the nozzle of the réellesprühenden polymer is additionally heated.
  • the present invention is therefore based on the object to provide a method by which a variety of thermoplastically processable materials can be applied in a desired, defined manner on various substrate surfaces in the form of a film.
  • the aforementioned object is achieved by a method for spray-coating substrate surfaces.
  • the essence of the invention consists essentially in that a thermoplastically processable material alone or as a compound in a mixture with other thermoplastically processable materials, with or without fillers is melted in an extruder, with an inorganic carrier gas or vapor under defined pressure set by pressed one or more hole nozzles as a mixture, relaxed to atmospheric pressure and cooled only on the substrate surface.
  • a compound is mixed directly in a twin-screw extruder.
  • this single-screw extruder is followed by a single-screw extruder or a melt pump.
  • thermoplastically processable materials such as single-component polymers, copolymers and terpolymers, as well as thermoplastically processable elastomers, in particular selected from acrylonitrile-butadiene-styrene (ABS), polyamide (PA), polylactate (PLA), Polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyetheretherketone (PEEK) and polyvinyl chloride (PVC), including their copolymers and compounds, which may contain further constituents, especially fillers.
  • ABS acrylonitrile-butadiene-styrene
  • PA polyamide
  • PLA polylactate
  • PMMA Polymethyl methacrylate
  • PC polycarbonate
  • PET polyethylene terephthalate
  • PE polyethylene
  • PE polypropylene
  • PS polystyrene
  • PEEK polyetheretherketone
  • high-performance materials such as PEEK can be sprayed with a high proportion of gas and a concomitant reduction in viscosity.
  • the amount of fillers can be varied freely within wide ranges, wherein the amount of fillers should preferably not exceed 80% by weight, based on the material, since cohesion of the coating can otherwise not be guaranteed.
  • the fillers may be inorganic in nature or polymers themselves which do not melt at the processing temperature, such as rubber, the fillers having no preferred direction.
  • fillers may be inorganic short fibers, polymeric fibers having a higher melting temperature than the processing temperature of the material or compound, and natural fibers.
  • thermoplastically processable material and / or the filler itself By changing the mixture over the spraying process, the thermoplastically processable material and / or the filler itself, as well as the ratio of thermoplastically processable material to filler, a layered different material structure can be produced.
  • carrier gas are inert, in particular inorganic gases or gas mixtures as well as steam.
  • inorganic gases or gas mixtures as well as steam.
  • the carrier gas or vapor is preferably used in a weight ratio of thermoplastically processable material to carrier gas or vapor in the range of 100 to 0.1 parts by weight to 100 to 30 parts by weight, in particular 100 to 0.3 to 100 to 15 parts by weight.
  • a spray is sprayed at a pressure of 10 to 500 bar, in particular 20 to 400 bar.
  • a pressurized heated gas preferably air must be supplied, which provides in an advantageous case to an additional atomization.
  • the nozzles are located, for example, on a flexible pressure tube and can be moved over the substrate surface by means of a robot be that a complete order with material is possible.
  • the nozzle (s) themselves is (are), for example, as a hole nozzle (s) formed with 1 to 50 openings, preferably 5 to 20 openings, with a diameter of 0.1 mm - 10 mm, but preferably 0.5 mm - 2 mm or openings with an equivalent cross-sectional area defined hole geometry of said opening diameter.
  • hot air spray gas
  • Slot nozzles can also be used, with the dimensions 0.1 - 3.0 x 3 - 30 mm, preferably 0.5 - 2.0 x 5 - 10 mm; In this case too, several slot nozzles can be arranged in the spray head.
  • carrier gas in the sense of the present invention comprises, in addition to the abovementioned substances and elements which are gaseous at room temperature (normal pressure) or the processing temperature, substances which form gaseous substances by a chemical or thermal reaction or are converted into the gaseous state , Particularly preferred in this sense is hot air.
  • the chemical composition of the spray gas which is preferably guided in the form of an annular nozzle around the outlet opening of the thermoplastic, may be the same or different from the carrier gas. Hot air is particularly preferred as the spray gas, which causes a further expansion of the carrier gas in the thermoplastic and a surface heating of the particles.
  • thermoplastically processable material used was a compound of 75% by weight of inorganic filler (barite) and 25% by weight of a commercially available plastic mixture of PE / EVA, white oil, flow additive and temperature stabilizer in granular form.
  • the output was 90 kg / h and the amount of gas (carrier gas) was 1.1 kg / h CO 2 .
  • the substrate surface used was a commercial compressed mixed fiber fleece.
  • Example 2 in principle, in this example in a second application substantially the same structure as in Example 1 was used.
  • the nozzle was changed.
  • BETE used in the heated air as a spray gas in an outer ring around the outlet nozzle around the mixture of carrier gas and compound heated.
  • the amount of carrier gas was reduced to 400 g / h.
  • the filler was reduced to 25 wt .-% and the amount of compound increased accordingly.
  • the output was 60 kg / h.
  • the amount of air used (spray gas) was 30 Nm 3 / h and was heated to 300 ° C.
  • the spray result was improved over Example 1.

Description

Gegenstand der Erfindung ist ein Verfahren zum Sprühbeschichten von Substratoberflächen, das es ermöglicht, unterschiedliche thermoplastisch verarbeitbare Werkstoffe auf verschiedenste Oberflächen mittels Sprühtechnologie aufzutragen.The invention relates to a method for spray coating of substrate surfaces, which makes it possible to apply different thermoplastically processable materials on a variety of surfaces by means of spray technology.

Zur Herstellung dünnwandiger, flächiger Bauteile oder beispielsweise Isolationen auf Textilien sind die unterschiedlichsten Verfahren bekannt. Diese Verfahren unterscheiden sich je nach Anwendung in der Formqualität, dem Material, einer Dickenverteilung über das Substrat (Bauteil) und der Technologie selbst.For the production of thin-walled, sheet-like components or, for example, insulation on textiles, a wide variety of methods are known. Depending on the application, these methods differ in the form quality, the material, a thickness distribution over the substrate (component) and the technology itself.

Bekannt sind die Verfahren des Tiefziehens, Vakuumtiefziehens und Pressens zur Verarbeitung von Folien zu Formteilen bzw. Einzelschichten.The methods of thermoforming, vacuum thermoforming and pressing for processing films into molded parts or individual layers are known.

Bei der Herstellung von flächigen Bauteilen mittels dieser Verfahren ist eine lokale Massenverteilung durch die Deformation der Folie bestimmt und kann nicht definiert eingestellt werden. Aus diesem Grund sind dann zum Beispiel so hergestellte Isolationen schwerer als sie aus akustischer, funktionaler Sicht benötigt werden. Dies behindert speziell in Fahrzeugen einen angestrebten Leichtbau.In the production of sheet-like components by means of these methods, a local mass distribution is determined by the deformation of the film and can not be set in a defined manner. For this reason, for example, then produced insulation heavier than they are needed from an acoustic, functional point of view. This hinders a targeted lightweight construction, especially in vehicles.

Zur stofflichen Abdichtung werden Folien auf die unterschiedlichsten Substrate durch Aufkleben oder Aufschmelzen aufgebracht.For material sealing films are applied to a variety of substrates by gluing or melting.

Zur partiellen Schallisolation werden aus akustischer Sicht sogenannte Schwerschichtfolien auf Teppich- oder Stirnwandbereiche aufgelegt, wo sie ankleben oder einschmelzen.For partial sound insulation so-called heavy-layer foils are placed on carpet or end wall areas from the acoustic point of view, where they stick or melt.

Bekannt sind weitere Verfahren zur Erzeugung von dünnen, flächigen Bauteilen für Kraftfahrzeuge, wie Schwerschichtbauteile für akustische Isolationsbauteile, unter anderem Stirnwände, die durch Spritzguss von thermo- und duroplastischen Materialien hergestellt werden.Other methods are known for producing thin, flat components for motor vehicles, such as heavy-layer components for acoustic insulation components, including end walls, which are produced by injection molding of thermosetting and thermosetting materials.

Das Spritzgießen (Thermoplast-Spritzgießen, oder Duroplast-Spritzgießen (Reaction Injection Moulding, RIM)) gestattet die Herstellung von Bauteilen mit unterschiedlichen, definierten Flächengewichten. Der hohe Invest der Anlagen wie auch der Werkzeuge begrenzt diese Verfahren auf hohe Stückzahlen.Injection molding (thermoplastic injection molding, or reaction injection molding (RIM)) allows the production of components with different, defined basis weights. The high investment of the equipment as well as the tools limits these procedures to high quantities.

Für das RIM-Verfahren besteht zusätzlich das Problem, dass das einzusetzende Material, beispielsweise Polyurethan, teuer ist und nicht rezykliert werden kann. Speziell für Isolationsbauteile in Fahrzeugen ist durch die Werkzeuggeometrie die Masseverteilung für alle Aufbauten festgelegt. Dies verhindert auch die gezielte akustische Optimierung einzelner Fahrzeugtypen (Motorvarianten) innerhalb einer Baureihe, die aus akustischer Sicht wünschenswert wäre.For the RIM process, there is the additional problem that the material to be used, for example polyurethane, is expensive and can not be recycled. Specifically for insulation components in vehicles, the tool geometry determines the mass distribution for all abutments. This also prevents the targeted acoustic optimization of individual vehicle types (engine variants) within a series that would be desirable from an acoustic point of view.

Bekannt sind weiter Verfahren zur Herstellung solcher flächiger Bauteile mittels Sintern von Pulver. Das Pulver wird auf ein warmes Abformwerkzeug aufgebracht, wo es durch Sintern eine Kunststoffschicht bildet, anschließend abgekühlt und das Bauteil entnommen wird. Diese Technologie ist zeit-, werkzeug- und energieintensiv. Damit bleibt dieses Verfahren auf die Herstellung hochwertiger Bauteile, wie Slushhäute beschränkt.Also known are methods for producing such flat components by sintering powder. The powder is applied to a warm molding tool where it is sintered by sintering Plastic layer forms, then cooled and the component is removed. This technology is time, tool and energy intensive. Thus, this process remains limited to the production of high-quality components, such as slush skins.

Bekannt sind Verfahren zur Beschichtung wie auch die Herstellung flächiger Bauteile mittels Sprühen. Das Sprühen thermoplastischer Kunststoffe geschieht entweder aus der Schmelze mittels einer oder mehrerer Düsen oder über "kaltes" Kunststoffpulver mittels Erwärmung über eine Flamme während der Flugphase und einem Trägergas oder direkt durch eine heiße Umgebung während der Flugphase. Diese Verfahren haben jedoch sehr geringe Durchsätze und sind bedingt zur Beschichtung von temperaturbeständigen Substraten geeignet. Bei einer Beschichtung von Textilien würden die hohen Temperaturen das Textilmaterial zerstören, bevor etwas aufgetragen ist.Are known methods for coating as well as the production of planar components by spraying. The spraying of thermoplastics is done either from the melt by means of one or more nozzles or "cold" plastic powder by heating a flame during the flight phase and a carrier gas or directly by a hot environment during the flight phase. However, these methods have very low throughputs and are conditionally suitable for coating temperature-resistant substrates. When coating textiles, the high temperatures would destroy the fabric before it has been applied.

Das Sprühverfahren findet auch Anwendung bei der Pulverregenerierung. In der DE 10 2005 050 890 A1 wird ein Verfahren und Vorrichtung zur Herstellung eines Nanokomposites beschrieben, bei dem die Trennung von Extraktions- und gegebenenfalls Dispersionsmittel von einer Polymerschmelze durch das Hochdrucksprühverfahren erfolgt. Hierbei erstarren die Polymertröpfchen schlagartig infolge der bei der Entspannung des hohen Druckniveaus auf Umgebungsdruck stattfindenden starken Abkühlung. Dabei entstehen die Nanokomposite.The spray process is also used in powder regeneration. In the DE 10 2005 050 890 A1 describes a method and apparatus for producing a nanocomposite, in which the separation of extraction and optionally dispersing agent from a polymer melt by the high-pressure spraying process takes place. This solidify the polymer droplets abruptly due to the taking place during the relaxation of the high pressure level to ambient pressure strong cooling. This produces the nanocomposites.

Als Schwerschicht zum Sprühen sind vernetzende Systeme auf PUR-Basis im Einsatz. Ausführungen finden sich hierzu in der DE 101 61 600 A1 und der DE 10 2005 058 292 A1 . Diese Materialien sind sehr preisintensiv und nicht rezyklierbar.As a heavy layer for spraying crosslinking systems are based on PUR in use. There are explanations for this in the DE 101 61 600 A1 and the DE 10 2005 058 292 A1 , These materials are very expensive and can not be recycled.

Weiterhin sind Verfahren und Vorrichtungen bekannt, bei denen ein Kunststoffstrang auf einer -meist vorbehandelten Substratoberflächeabgelegt wird. In EP 0 524 092 B2 wird ein Verfahren und Vorrichtung zum Herstellen eines Artikels mit einem ausgeformten Profilstrang beschrieben. Hierbei wird der Profilstrang durch einen Extrusionskopf, der mit dem Extruder über einen beheizten flexiblen Druckschlauch verbunden ist, erzeugt und abgelegt.Furthermore, methods and devices are known in which a plastic strand is deposited on a mostly pretreated substrate surface. In EP 0 524 092 B2 For example, a method and apparatus for making an article having a molded tread is described. Here, the profile strand is produced and deposited by an extrusion head which is connected to the extruder via a heated flexible pressure hose.

DE 30 47 727 C2 beschreibt ein Verfahren zur Herstellung von dünnen Schutzfilmen durch Aufsprühen von verflüssigtem thermoplastischem Material. Das hier beschriebene Verfahren soll den Einsatz herkömmlicher Heißspritzgeräte, in der Spritzwerkstoff geschmolzen und somit verflüssigt wird, ermöglichen, der dann unmittelbar auf die schützende Oberfläche aufgetragen werden kann. Es wird weiterhin beschrieben, dass die Tendenz dieser Materialien, nach Auftreffen auf die Oberfläche Kügelchen zu bilden, bisher keinen genügend homogenen Film ergab, jedoch soll gemäß dieser Beschreibung in einfachster Weise durch einen gleichzeitigen oder anschließenden Sintervorgang begegnet werden. Für das Sintern des thermoplastischen Materials hat es sich demgemäß als vorteilhaft gezeigt, wenn das Sintern durch Erwärmen des aufgesprühten thermoplastischen Materials durchgeführt wird, um so zu einem gleichmäßigen glatten und porenfreien Auftrag zu gelangen. Die für das Sintern erforderliche Wärme kann dem thermoplastischen Material von außen durch Wärmestrahlung, Warmluftzufuhr oder dergleichen zugeführt werden. Zweckmäßig kann es sein, das thermoplastische Material auf eine zuvor erhitzte Oberfläche zu sprühen, so dass der Sintervorgang gleichzeitig mit einem Aufsprühen erfolgen und somit ein zeitlicher optimaler Verfahrensablauf erhalten wird. Der nach dem Auftreffen des Materials auf der Oberfläche vorgenommene Sintervorgang ist jedoch sehr aufwendig und belastet das Substratmaterial thermisch erneut. DE 30 47 727 C2 describes a process for producing thin protective films by spraying liquefied thermoplastic material. The method described here is intended to enable the use of conventional hot spraying equipment, in which spray material is melted and thus liquefied, which can then be applied directly to the protective surface. It is further described that the tendency of these materials to form beads after hitting the surface has not heretofore yielded a sufficiently homogeneous film, but according to this description, it is most convenient to address them by a simultaneous or subsequent sintering operation. For the sintering of the thermoplastic material, it has accordingly been found to be advantageous if the sintering is carried out by heating the sprayed-on thermoplastic material so as to obtain a uniform, smooth and nonporous application. The heat required for sintering can be supplied to the thermoplastic material from the outside by heat radiation, hot air supply or the like. It may be useful, the thermoplastic material to a previously to spray heated surface, so that the sintering process is carried out simultaneously with a spraying and thus a temporally optimal process flow is obtained. However, the sintering process carried out after the impact of the material on the surface is very complicated and thermally re-stresses the substrate material.

DT 16 46 051 B2 beschreibt ein Verfahren zum Aufbringen polymerer Überzüge auf feste Oberflächen durch Aufsprühen eines geschmolzenen thermoplastischen Polymerisats. Danach wird das Schmelzen des Polymerisats und die Zuführung der Schmelze in einem Pressgasstrom nach dem Spritzdruckverfahren durchgeführt und der versprühte Gas/Polymerisat-Strahl während seines Weges zu der zu beschichtenden Oberfläche einer Wärmestrahlbehandlung unterzogen. Es wird beschrieben, das thermoplastische Polymerisat beliebiger Korngröße in Extrudern oder Kolbenzylindern-Einrichtungen in den geschmolzenen Zustand zu überführen und mittels Pressgas mit Hilfe einer Drucklufteinspritzdüse in Form eines durch einen Wärmestrahlstrom beheizten Gas/Polymerisat-Strahls auf die zu beschichtende Oberfläche aufzusprühen, die zuvor erwärmt wird.DT 16 46 051 B2 describes a process for applying polymeric coatings to solid surfaces by spraying a molten thermoplastic polymer. Thereafter, the melting of the polymer and the supply of the melt in a compressed gas stream is carried out by the injection pressure method and subjected to the sprayed gas / polymer beam during its path to the surface to be coated, a heat radiation treatment. It is described to convert the thermoplastic polymer of any particle size in extruders or piston-cylinder devices in the molten state and sprayed by means of compressed air by means of a compressed air injection nozzle in the form of a heated by a heat flow gas / polymer jet on the surface to be coated, which previously heated becomes.

DE 32 25 844 A1 beschreibt ein Verfahren und eine Vorrichtung zum Auftragen von Schichten aus thermoplastischen Kunststoffen oder Heißschmelzklebstoffen. Beschrieben wird ein Verfahren zum Auftragen von Schichten aus thermoplastischem Kunststoffen oder Heißschmelzklebstoffen, bei dem der eingesetzte Kunststoff bzw. Heißschmelzklebstoff aufgeschmolzen, dann zerstäubt und versprüht wird. Vorzugsweise wird hier die Temperatur des geschmolzenen Kunststoffs bzw. Heißschmelzklebstoffs bis zum Moment seines Versprühens konstant gehalten. Die Vorrichtung zur Durchführung des Verfahrens enthält eine beheizbare Schmelzeinrichtung für einen Kunststoff- oder Heißschmelzklebstoff, eine eine Düse aufweisende beheizbare Sprühvorrichtung, eine beheizbare Zuführvorrichtung des geschmolzenen Materials in die Sprühvorrichtung, ein Temperaturmess- und Temperaturregelsystem sowie Regelsysteme für die Zufuhr und Abgabe eines geschmolzenen Materials und ggf. des erhitzten Sprühgases. Dadurch lassen sich zwei- oder dreidimensionale Gegenstände beliebiger Art und Gestalt von außen und/oder innen mit einer beliebig starken gleichmäßigen oder musterförmigen Schicht versehen. DE 32 25 844 A1 describes a method and apparatus for applying layers of thermoplastic or hot melt adhesives. A method is described for applying layers of thermoplastic materials or hot-melt adhesives, in which the plastic or hot-melt adhesive used is melted, then atomized and sprayed. Preferably, the temperature of the molten plastic or hot melt adhesive is kept constant until the moment of spraying. The device for carrying out the Method includes a heatable melting device for a plastic or hot melt adhesive, a nozzle having a heated spray device, a heatable feeder of the molten material in the spray device, a temperature measuring and temperature control system and control systems for the supply and delivery of a molten material and possibly the heated spray gas , As a result, two- or three-dimensional objects of any type and shape can be provided with an arbitrarily strong uniform or patterned layer from the outside and / or inside.

DE 42 31 074 A1 beschreibt die Verwendung von Kunststoffpulvern als Füllstoff in sprüh- und spritzfähigen Beschichtungsmassen, Lacken und Dichtmassen. Beschrieben wird die Verwendung von Pulvern des Dichtebereichs 0,1 bis 2,0 g/cm3 einer mittleren Korngröße von maximal 0,2 mm, die durch mechanische Zerkleinerung von gegebenenfalls mineralische Füllstoffe enthaltenden, festen Kunststoffen erhalten worden sind, als Füllstoff, gegebenenfalls neben weiteren Füllstoffen in sprüh- und spritzfähigen Lacken, Beschichtungs- und Dichtemassen auf Basis von Ein- oder Zweikomponenten-Polyurethan-Bindemitteln. DE 42 31 074 A1 describes the use of plastic powders as filler in sprayable and sprayable coating materials, paints and sealants. Described is the use of powders of the density range 0.1 to 2.0 g / cm 3 of a mean particle size of not more than 0.2 mm, which have been obtained by mechanical comminution of optionally mineral fillers, solid plastics, as a filler, optionally in addition other fillers in sprayable and sprayable paints, coating and sealing compounds based on one- or two-component polyurethane binders.

DE 101 61 600 A1 beschreibt ein Verfahren zum Aufsprühen von Kunststoffschichten. Beschrieben wird ein Verfahren und eine Vorrichtung zum Aufbringen einer füllstoffhaltigen Kunststoffschicht auf eine geformte Oberfläche, wobei eine Mischung, enthaltend Bindergemisch, Feststoffförderer und Füllstoff, auf die geformte Oberfläche aufgesprüht wird, in dem man zunächst aus einer Mischung, enthaltend Bindergemisch und Feststoffförderer, eine Freistrahl zum Sprühauftrag erzeugt und den Füllstoff anschließend in den Freistrahl der noch nicht aus polymerisierten Bindermischung zudosiert. Das Verfahren eignet sich besonders zum Sprühauftrag von Schwerschichten, wie sin in herkömmlichen Masse-Feder-Systemen eingesetzt werden. DE 101 61 600 A1 describes a method for spraying plastic layers. Disclosed is a method and apparatus for applying a filler-containing plastic layer to a shaped surface, wherein a mixture containing binder mixture, solids promoter and filler is sprayed onto the shaped surface by first blasting a mixture containing binder mixture and solids promoter to the Spray application produced and then added the filler in the free jet of not yet polymerized binder mixture. The method is particularly suitable for the spray application of heavy layers, as sin are used in conventional mass-spring systems.

DE 10 2005 058 292 A1 beschreibt ein Verfahren und eine Vorrichtung zur Herstellung von beschichteten Formteilen. Hier wird ein Verfahren und eine Vorrichtung zur Herstellung von Formteilen, enthaltend eine Schicht aus Polyurethan im Schussbetrieb, bei dem die Reaktivkomponenten mit einer zylindrischen Mischkammer vermischt werden und das erzeugte Reaktivgemisch anschließend durch einen Strömungskanal fließt und auf die Oberflächen eines Substrats aufgesprüht wird und darauf aushärtet und anschließend der Strömungskanal durch einen Gasstrom gereinigt wird. DE 10 2005 058 292 A1 describes a method and an apparatus for producing coated moldings. Here, a method and an apparatus for producing molded parts, comprising a layer of polyurethane in the weft operation, in which the reactive components are mixed with a cylindrical mixing chamber and the reactive mixture produced then flows through a flow channel and is sprayed onto the surfaces of a substrate and cured and then the flow channel is cleaned by a gas stream.

US 5,605,720 A beschreibt ein kontinuierliches Inline-Verfahren zur Herstellung und Anwendung von Heiß-Schmelzklebern auf ein Substrat durch Dosierung eines Polymerklebers und eines Klebrigmachers in einem bestimmten Gewichtsverhältnis in einem Extruder, in dem diese Rohmaterialien eine homogene Schmelze bilden. Die Schmelze wird kontinuierlich direkt in einen Heiß-Schmelz-Applikator gegeben und auf ein Substrat aufgebracht. US 5,605,720 A describes a continuous in-line process for preparing and applying hot melt adhesives to a substrate by dosing a polymer adhesive and a tackifier in a particular weight ratio in an extruder in which these raw materials form a homogeneous melt. The melt is continuously added directly to a hot melt applicator and applied to a substrate.

CH 497 291 A bezieht sich auf Verfahren zum Aufbringen von Überzügen aus polymeren Materialien auf die Oberfläche von Erzeugnissen durch Aufsprühen, in dem das Polymere auf eine Temperatur, welche höher als dessen Schmelzpunkt liegt, erhitzt und die erhaltene Schmelze mit Hilfe von Pressgas auf die zu überziehende Erzeugnisoberfläche aufgesprüht wird, wobei man den aus der Düse ausfließenden Strahl des aufzusprühenden Polymeren zusätzlich erwärmt. CH 497 291 A relates to methods for applying coatings of polymeric materials to the surface of products by spraying, in which the polymer is heated to a temperature which is higher than its melting point, and the melt obtained by means of compressed gas to be coated on the Produced surface is sprayed, wherein the jet flowing out of the nozzle of the aufzusprühenden polymer is additionally heated.

Der vorliegenden Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren bereitzustellen, mit dem die unterschiedlichsten thermoplastisch verarbeitbaren Werkstoffe in gewünschter, definierter Weise auf verschiedenartige Substratoberflächen in Form eines Films aufgebracht werden können.The present invention is therefore based on the object to provide a method by which a variety of thermoplastically processable materials can be applied in a desired, defined manner on various substrate surfaces in the form of a film.

Erfindungsgemäß wird die vorgenannte Aufgabe gelöst durch ein Verfahren zum Sprühbeschichten von Substratoberflächen.According to the invention, the aforementioned object is achieved by a method for spray-coating substrate surfaces.

Der Kern der Erfindung besteht im Wesentlichen darin, dass ein thermoplastisch verarbeitbarer Werkstoff alleine oder als Compound in einer Mischung mit anderen thermoplastisch verarbeitbaren Werkstoffen, mit oder ohne Füllstoffe in einem Extruder aufgeschmolzen wird, mit einem anorganischen Trägergas oder -dampf unter definierten Druck gesetzt, durch eine oder mehrere Lochdüsen als Gemisch gepresst, auf Atmosphärendruck entspannt und erst auf der Substratoberfläche abgekühlt wird.The essence of the invention consists essentially in that a thermoplastically processable material alone or as a compound in a mixture with other thermoplastically processable materials, with or without fillers is melted in an extruder, with an inorganic carrier gas or vapor under defined pressure set by pressed one or more hole nozzles as a mixture, relaxed to atmospheric pressure and cooled only on the substrate surface.

In einer speziellen Ausführung wird ein Compound in einem Doppelschneckenextruder direkt gemischt. In einer weiteren Ausführung schließt sich beispielsweise an diesen Doppelschneckenextruder ein Einschneckenextruder oder eine Schmelzepumpe an.In a special version, a compound is mixed directly in a twin-screw extruder. In a further embodiment, for example, this single-screw extruder is followed by a single-screw extruder or a melt pump.

Als Materialen zum Versprühen sind praktisch alle thermoplastisch verarbeitbaren Werkstoffe einsetzbar, unabhängig davon, ob sie als Homopolymer oder als Compound, ungefüllt oder mit nichtschmelzenden Stoffen gefüllt, vorliegen. Besonders bevorzugt im Sinne der vorliegenden Erfindung sind thermoplastisch verarbeitbare Werkstoffe, wie Einstoff-Polymere, Co- und Terpolymere als auch thermoplastisch verarbeitbare Elastomere, insbesondere ausgewählt aus, Acrylnitril-Butadien-Styrol (ABS), Polyamid (PA), Polylactat (PLA), Polymethylmethacrylat (PMMA), Polycarbonat (PC), Polyethylenterephthalat (PET), Polyethylen (PE), Polypropylen (PP), Polystyrol (PS), Polyetheretherketon (PEEK) und Polyvinylchlorid (PVC) einschließlich deren Copolymere und Compounds, die gegebenenfalls weitere Bestandteile, insbesondere Füllstoffe enthalten. In einer speziellen Ausführungsform auch können mit hohem Anteil an Gas und einer damit verbundenen Viskositätsverringerung Hochleistungswerkstoffe wie beispielsweise PEEK versprüht werden. Die Menge der Füllstoffe kann in weiten Bereichen frei variiert werden, wobei die Menge der Füllstoffe vorzugsweise 80 Gew. %, bezogen auf den Werkstoff nicht überschreiten sollte, da der Zusammenhalt der Beschichtung sonst nicht gewährleistet werden kann.As materials for spraying virtually all thermoplastically processable materials are used, regardless of whether they are present as a homopolymer or as a compound, unfilled or filled with non-melting substances. Particularly preferred for the purposes of the present invention are thermoplastically processable materials, such as single-component polymers, copolymers and terpolymers, as well as thermoplastically processable elastomers, in particular selected from acrylonitrile-butadiene-styrene (ABS), polyamide (PA), polylactate (PLA), Polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyetheretherketone (PEEK) and polyvinyl chloride (PVC), including their copolymers and compounds, which may contain further constituents, especially fillers. In a specific embodiment, high-performance materials such as PEEK can be sprayed with a high proportion of gas and a concomitant reduction in viscosity. The amount of fillers can be varied freely within wide ranges, wherein the amount of fillers should preferably not exceed 80% by weight, based on the material, since cohesion of the coating can otherwise not be guaranteed.

Die Füllstoffe können anorganischer Natur oder Polymere selbst, die bei Verarbeitungstemperatur nicht schmelzen, wie z B. Gummi sein, wobei die Füllstoffe keine Vorzugsrichtung besitzen. Des Weiteren können als Füllstoffe anorganische Kurzfasern, polymere Fasern mit einer höheren Schmelztemperatur als die Verarbeitungstemperatur des Werkstoffs oder des Compounds sowie natürliche Fasern eingesetzt werden.The fillers may be inorganic in nature or polymers themselves which do not melt at the processing temperature, such as rubber, the fillers having no preferred direction. In addition, fillers may be inorganic short fibers, polymeric fibers having a higher melting temperature than the processing temperature of the material or compound, and natural fibers.

Durch die Änderung der Mischung über den Sprühvorgang, des thermoplastisch verarbeitbaren Werkstoffes und/oder des Füllstoffes selbst, sowie des Verhältnisses von thermoplastisch verarbeitbarem Werkstoff zu Füllstoff, kann ein schichtweise unterschiedlicher Materialaufbau erzeugt werden.By changing the mixture over the spraying process, the thermoplastically processable material and / or the filler itself, as well as the ratio of thermoplastically processable material to filler, a layered different material structure can be produced.

Als Trägergas bieten sich inerte, insbesondere anorganische Gase oder Gasgemische als auch Dampf an. Besonders bevorzugt im Sinne der Erfindung wird beispielsweise Stickstoff, Kohlenstoffdioxid, Luft oder Wasser, bei dieser Temperatur gasförmig, eingesetzt.As a carrier gas are inert, in particular inorganic gases or gas mixtures as well as steam. For the purposes of the invention, nitrogen, carbon dioxide, air or water, for example, is used in gaseous form at this temperature.

Das Trägergas oder -dampf wird bevorzugt in einem Gewichtsverhältnis von thermoplastisch verarbeitbarem Werkstoff zu Trägergas oder - dampf im Bereich von 100 zu 0,1 Gewichtsteilen bis 100 zu 30 Gewichtsteilen, insbesondere 100 zu 0,3 bis 100 zu 15 Gewichtsteilen eingesetzt. Vorzugsweise wird ein Sprühstrahl mit einem Druck von 10 bis 500 bar, insbesondere 20 bis 400 bar versprüht.The carrier gas or vapor is preferably used in a weight ratio of thermoplastically processable material to carrier gas or vapor in the range of 100 to 0.1 parts by weight to 100 to 30 parts by weight, in particular 100 to 0.3 to 100 to 15 parts by weight. Preferably, a spray is sprayed at a pressure of 10 to 500 bar, in particular 20 to 400 bar.

Mit steigendem Druck verringert sich die Tröpfchengröße; der Materialauftrag wird dadurch homogener. Mit steigendem Druck kühlt das jedoch das Material beim Expandieren und Entspannen stärker ab. Dies führt materialabhängig dazu, dass kein Verbund mit der Substratoberfläche mehr erzielt wird. In diesem Fall muss dann ein unter Druck stehendes erwärmtes Gas (Sprühgas), bevorzugt Luft zugeführt werden, welches im günstigen Fall zu einer zusätzlichen Versprühung sorgt.As the pressure increases, the droplet size decreases; The material application is thus more homogeneous. As the pressure increases, however, the material cools down more during expansion and relaxation. Depending on the material, this means that no bond with the substrate surface is achieved any more. In this case, then a pressurized heated gas (spray gas), preferably air must be supplied, which provides in an advantageous case to an additional atomization.

Die Düsen befinden sich beispielsweise an einem flexiblen Druckrohr und können mittels Roboter so über die Substratoberfläche bewegt werden, dass ein vollständiger Auftrag mit Material möglich ist. Die Düse(n) selbst ist (sind) beispielsweise als Lochdüse(n) ausgebildet mit 1 bis 50 Öffnungen, bevorzugt 5 bis 20 Öffnungen, mit einem Durchmesser von 0,1 mm - 10 mm, bevorzugt jedoch 0,5 mm - 2 mm oder Öffnungen mit einer äquivalenten Querschnittsfläche definierter Lochgeometrie der genannten Öffnungsdurchmesser. Zum zusätzlichen Erwärmen kann heiße Luft (Sprühgas) eingebracht werden.The nozzles are located, for example, on a flexible pressure tube and can be moved over the substrate surface by means of a robot be that a complete order with material is possible. The nozzle (s) themselves is (are), for example, as a hole nozzle (s) formed with 1 to 50 openings, preferably 5 to 20 openings, with a diameter of 0.1 mm - 10 mm, but preferably 0.5 mm - 2 mm or openings with an equivalent cross-sectional area defined hole geometry of said opening diameter. For additional heating hot air (spray gas) can be introduced.

Auch können Schlitzdüsen zum Einsatz kommen, mit den Abmessungen 0,1 - 3,0 x 3 - 30 mm, bevorzugt 0,5 - 2,0 x 5 - 10 mm; auch hierbei können mehrere Schlitzdüsen im Sprühkopf angeordnet sein.Slot nozzles can also be used, with the dimensions 0.1 - 3.0 x 3 - 30 mm, preferably 0.5 - 2.0 x 5 - 10 mm; In this case too, several slot nozzles can be arranged in the spray head.

Der Begriff des Trägergases im Sinne der vorliegenden Erfindung umfasst neben den oben genannten Stoffen und Elementen, die bei Raumtemperatur (Normaldruck) oder der Verarbeitungstemperatur gasförmig sind auch solche Stoffe, die durch eine chemische oder thermische Reaktion gasförmige Stoffe bilden oder in den gasförmigen Zustand überführt werden. Besonders bevorzugt in diesem Sinne ist heiße Luft.The term carrier gas in the sense of the present invention comprises, in addition to the abovementioned substances and elements which are gaseous at room temperature (normal pressure) or the processing temperature, substances which form gaseous substances by a chemical or thermal reaction or are converted into the gaseous state , Particularly preferred in this sense is hot air.

Die chemische Zusammensetzung des Sprühgases, das vorzugsweise in Form einer Ringdüse um die Austrittsöffnung des Thermoplasten herumgeführt wird, kann gleich dem Trägergas oder davon verschieden sein. Besonders bevorzugt ist heiße Luft als Sprühgas, das ein weiteres Expandieren des Trägergases im Thermoplasten und eine Oberflächenerwärmung der Partikel bewirkt.The chemical composition of the spray gas, which is preferably guided in the form of an annular nozzle around the outlet opening of the thermoplastic, may be the same or different from the carrier gas. Hot air is particularly preferred as the spray gas, which causes a further expansion of the carrier gas in the thermoplastic and a surface heating of the particles.

Nachfolgend wird die Erfindung anhand von zwei Beispielen erläutert.The invention will be explained below with reference to two examples.

Ausführungsbeispiele:EXAMPLES Beispiel 1:Example 1:

Anwendung fanden handelsübliche Extruder KraussMaffei Bernstorff ZE40 Ax29D und KE90x30D in Reihe geschaltet; jeweils ausgerüstet mit speziell ausgelegten Schnecken. Das Werkzeug war ein Einfachrohrkopf mit 24 Lochdüsen von jeweils 1,1 mm Lochdurchmesser, zweireihig angeordnet.Commercial extruders KraussMaffei Bernstorff ZE40 Ax29D and KE90x30D were used in series; each equipped with specially designed screws. The tool was a single tube head with 24 hole nozzles, each with a 1.1 mm hole diameter, arranged in two rows.

Als thermoplastisch verarbeitbaren Werkstoff wurde ein Compound von 75 Gew. % anorganischem Füllstoff (Schwerspat) und 25 Gew. % eines handelsüblichen Kunststoffgemischs aus PE/EVA, Weißöl, Fließadditiv und Temperaturstabilisierer in Granulatform angewendet.The thermoplastically processable material used was a compound of 75% by weight of inorganic filler (barite) and 25% by weight of a commercially available plastic mixture of PE / EVA, white oil, flow additive and temperature stabilizer in granular form.

Die Ausstoßleistung betrug 90 kg/h und die Gasmenge (Trägergas) lag bei 1,1 kg/h CO2. Als Substratoberfläche diente ein handelsübliches verpresstes Mischfaservlies.The output was 90 kg / h and the amount of gas (carrier gas) was 1.1 kg / h CO 2 . The substrate surface used was a commercial compressed mixed fiber fleece.

Mit diesen Einstellungen wurde ein gutes Sprühverhalten erzielt und eine biegeweiche Kunststoffschicht auf der textilen Oberfläche hergestellt.With these settings, a good spraying behavior was achieved and a flexible plastic layer was produced on the textile surface.

Beispiel 2:Example 2:

Prinzipiell wurde in diesem Beispiel in einer zweiten Anwendung im Wesentlichen der gleiche Aufbau wie im Beispiel 1 verwendet. Geändert wurde die Düse. Hier wurde eine Rundstrahldüse der Fa. BETE verwendet, bei der erwärmte Luft als Sprühgas in einem äußeren Ring um die Austrittsdüse herum das Gemisch aus Trägergas und Compound erwärmte. Die Menge des Trägergases wurde auf 400g/h reduziert. Beim eingesetzten Material wurde der Füllstoff auf 25 Gew.-% reduziert und die Menge an Compound entsprechend erhöht.In principle, in this example in a second application substantially the same structure as in Example 1 was used. The nozzle was changed. Here was a round jet nozzle Fa. BETE used in the heated air as a spray gas in an outer ring around the outlet nozzle around the mixture of carrier gas and compound heated. The amount of carrier gas was reduced to 400 g / h. In the material used, the filler was reduced to 25 wt .-% and the amount of compound increased accordingly.

Die Ausstoßleistung betrug 60 kg/h. Die eingesetzte Luftmenge (Sprühgas) betrug 30 Nm3/h und war auf 300°C erwärmt. Das Sprühergebnis war gegenüber Beispiel 1 verbessert.The output was 60 kg / h. The amount of air used (spray gas) was 30 Nm 3 / h and was heated to 300 ° C. The spray result was improved over Example 1.

Claims (16)

  1. A method for spray-coating substrate surfaces, in which
    (a) a thermoplastically processable material containing a filler, wherein the amount of said filler does not exceed 80% by weight, is molten and thus liquefied in an extruder in a first step;
    (b) the molten material is pressurized by means of a carrier gas;
    (c) a mixture formed from the molten material, the filler and the carrier gas is pressed through one or more nozzles, wherein a spraying gas having a temperature that is at least as high as the melt temperature is supplied to the spray jet in the region of the outlet aperture of the nozzle; and
    (d) the obtained spray jet with the molten thermoplastically processable material and the filler is directed onto the substrate surface, wherein the material impinges in drops in a flowable state onto the substrate surface, forms a continuous coating on the substrate surface, and subsequently solidifies.
  2. The process according to claim 1, characterized in that said thermoplastically processable material is selected from homopolymers, co- and terpolymers or thermoplastically processable elastomers, especially acrylonitrile-butadienestyrene (ABS), polyamide (PA), polylactate (PLA), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyether ether ketone (PEEK) and polyvinyl chloride (PVC) including copolymers and compounds thereof, which may optionally contain further components, especially fillers.
  3. The process according to claim 1 or 2, characterized in that said filler is inorganic in nature.
  4. The process according to any of claims 1 to 3, characterized in that said filler is in the form of an inorganic short fiber.
  5. The process according to any of claims 1 to 4, characterized in that said filler has polymeric fibers having a melting temperature higher than the processing temperature of the compound.
  6. The process according to any of claims 1 to 5, characterized in that said filler comprises natural fibers.
  7. The process according to any of claims 1 to 6, characterized in that the mixture, the thermoplastically processable material and/or the filler itself as well as the weight ratio of thermoplastically processable material to filler are varied in the course of the spraying process.
  8. The process according to any of claims 1 to 7, characterized in that nitrogen, carbon dioxide or air is employed as the carrier gas and/or spraying gas.
  9. The process according to any of claims 1 to 8, characterized in that a spraying jet with a weight ratio of thermoplastically processable material to carrier gas within a range of from 100:0.1 weight parts to 100:30 weight parts, especially from 100:0.3 to 100:15 weight parts, is employed.
  10. The process according to any of claims 1 to 9, characterized in that a spray jet with a pressure of from 10 to 500 bar, especially from 20 to 400 bar, is employed.
  11. The process according to any of claims 1 to 10, characterized in that from 1 to 50, especially from 5 to 20, nozzles with different output cross-sectional areas are employed.
  12. The process according to any of claims 1 to 11, characterized in that said mixture is pressed through orifice and/or slotted nozzles.
  13. The process according to any of claims 1 to 12, characterized in that orifice nozzles with the same or different diameters within a range of from 0.1 mm to 10 mm, preferably from 0.5 mm to 2 mm, or discharge openings with comparable cross-sectional areas are employed.
  14. The process according to any of claims 1 to 13, characterized in that slotted nozzles with the same or different cross-sectional areas of 0.1-3 mm x 3-30 mm, especially 0.5-2 mm x 5-10 mm, are employed.
  15. The process according to any of claims 1 to 14, characterized in that a continuous coating that is porous or coherent in itself is prepared.
  16. The process according to any of claims 1 to 15, characterized in that a substrate selected from textiles or a mold cavity with or without a surface structure is employed.
EP14725032.8A 2013-05-06 2014-05-06 Spray-coating method Active EP2994242B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013208235.5A DE102013208235A1 (en) 2013-05-06 2013-05-06 Method for spray coating
PCT/EP2014/059180 WO2014180817A1 (en) 2013-05-06 2014-05-06 Spray-coating method

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CN109622320A (en) * 2018-11-30 2019-04-16 长春汽富维东阳汽车塑料零部件有限公司 Bumper spraying method
RU2715169C1 (en) * 2019-10-04 2020-02-25 Федеральное государственное бюджетное научное учреждение "Федеральный научный агроинженерный центр ВИМ" (ФГБНУ ФНАЦ ВИМ) Device for sputtering of ultrahigh molecular polyethylene
CN111013883A (en) * 2019-11-25 2020-04-17 浙江明泉工业涂装有限公司 Robot control method for intelligent spraying of multiple vehicle types
EP4352801A2 (en) * 2021-06-02 2024-04-17 National University of Singapore Apparatus and method for production of sulfur-host composite materials

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2437263A (en) * 1948-03-09 Fred w
CH497291A (en) * 1967-08-23 1970-10-15 Otdel Mek Polimerov An Bssr Applying a coating of molten plastics by inert gas
DE1646051B2 (en) * 1967-09-06 1977-01-20 Otdel mechaniki polimerow Akademii Nauk, BSSR, Gome] (Sowjetunion) METHOD OF APPLYING POLYMERIC COATINGS TO SOLID SURFACES BY SPRAYING ON A MOLTEN THERMOPLASTIC POLYMERIZATE
DE3047727A1 (en) * 1980-12-18 1982-07-15 Heibey, Friedrich, Dr., 2000 Hamburg "METHOD FOR THE PRODUCTION OF THIN PROTECTIVE FILMS BY SPRAYING ON LIQUID THERMOPLASTIC MATERIAL AND THEREFORE PROTECTIVE FILM THICK FILM"
DE3225844C2 (en) * 1982-07-09 1985-06-20 Sprimag Spritzmaschinenbau Gmbh, 7312 Kirchheim Method and device for applying layers of thermoplastics
DE3543469A1 (en) * 1985-12-09 1987-06-11 Henning J Claassen SPRAYING HEAD FOR SPRAYING A THERMOPLASTIC PLASTIC, ESPECIALLY A MELTING ADHESIVE
JPH01225656A (en) * 1988-03-07 1989-09-08 Japan Synthetic Rubber Co Ltd Thermoplastic polymer composition
CA1336373C (en) * 1988-09-21 1995-07-25 Nordson Corporation Apparatus for spraying hot melt adhesives
DE4123588A1 (en) 1991-07-17 1993-01-21 Ver Glaswerke Gmbh METHOD AND DEVICE FOR PRODUCING A VEHICLE WINDOW
RU2004347C1 (en) * 1991-12-29 1993-12-15 Алексей Иванович Степаков Fluid material sprayer
DE4231074A1 (en) * 1992-09-17 1994-03-24 Bayer Ag Use of plastic powders as filler in sprayable and sprayable coating compounds, lacquers and sealing compounds
US5605720A (en) * 1996-04-04 1997-02-25 J & M Laboratories Inc. Method of continuously formulating and applying a hot melt adhesive
US6488773B1 (en) * 1999-02-19 2002-12-03 Plastic Stuff, Llc Apparatus and method for spraying polymer
RU2213805C2 (en) * 2001-10-23 2003-10-10 Крыса Валерий Корнеевич Method of application of coats made from powder materials and device for realization of this method
DE10161600A1 (en) * 2001-12-14 2003-07-03 Stankiewicz Gmbh Process for spraying plastic layers
DE102005050890A1 (en) 2005-10-21 2007-04-26 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Producing a nano-composite, useful e.g. as coating, comprises contacting a nano-particle and a dispersing agent containing nano-particle dispersion with e.g. a supercritical liquid extracting agent and a polymer melt
DE102005058292A1 (en) 2005-12-07 2007-06-14 Hennecke Gmbh Method and device for the production of coated molded parts

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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DE102013208235A1 (en) 2014-11-06
CN105339095A (en) 2016-02-17
KR20160007551A (en) 2016-01-20
EP2994242A1 (en) 2016-03-16
US20160108511A1 (en) 2016-04-21
RU2015152031A (en) 2017-06-14
WO2014180817A1 (en) 2014-11-13
RU2650520C2 (en) 2018-04-16

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