US20070116947A1 - UV-Curing Anti-Fingerprinting Coatings - Google Patents

UV-Curing Anti-Fingerprinting Coatings Download PDF

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Publication number
US20070116947A1
US20070116947A1 US11/626,729 US62672907A US2007116947A1 US 20070116947 A1 US20070116947 A1 US 20070116947A1 US 62672907 A US62672907 A US 62672907A US 2007116947 A1 US2007116947 A1 US 2007116947A1
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United States
Prior art keywords
meth
coating material
layer
metal surface
acrylates
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Abandoned
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US11/626,729
Inventor
Karsten Hackbarth
Matthias Koch
Kerstin Motzkat
Joerg Sander
Holger Endres
Wolfgang Schneider
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Individual
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Individual
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Priority to US11/626,729 priority Critical patent/US20070116947A1/en
Publication of US20070116947A1 publication Critical patent/US20070116947A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/064—Polymers containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers

Definitions

  • the present invention relates to a process for producing stain-resistant function coatings for metal surfaces, in particular aluminum or high-grade steel surfaces, as well as suitable coating materials for these.
  • high-grade steel is preferably used.
  • This is frequently used with a polished or brushed surface and without additional coatings.
  • metallic parts having very different compositions are also used in architecture, for interior fittings of buildings, in furniture-making as well as for ornamental applications. In these cases, too, the surface of the metal is frequently polished, brushed or otherwise provided with surface patterns and is used without the application of further coatings.
  • the metal surface is highly susceptible to soiling by dust, food or cleaning agents, or marking by fingerprints.
  • a number of methods of treating the surfaces of metals in order to improve the scratch resistance of the surface or to avoid soiling have already been proposed. These involve coating processes using solvent-based and aqueous systems, for example, aqueous electrophoretically precipitable dip coatings, or powder coatings. These coatings are intended to improve the soiling behavior and the scratch resistance of the surface. Disadvantages of the processes are, for example, the curing conditions, such as time, temperature, as well as the consequent plant dimensions. Moreover, it is frequently impossible to form the objects without destroying the surface coating.
  • EP 1 036 829 deals with UV-cross-linkable coating materials for metals and conductive plastics, but describes only aqueous systems, which are applied to electrically conducting substrates by means of electrophoretic coating and are subsequently first of all dried at elevated temperature, then post-cured under UV light.
  • JP-A-07/171496 and JP-A-04/150976 (1992) describe heat-curable coatings on high-grade steel which are produced from polyester resins and silicate resin or melamine resin.
  • JP 10/228446 and EP 0 789 065 describe special UV-cross-linking coating systems substantially for coating wood, which are applied in layers of above 20 or 30 ⁇ m.
  • the coated surface should have a good stain resistance and be scratch resistant; in addition, the natural appearance in particular of brushed or otherwise structured metal surfaces should be preserved. No observations about these requirements are made in prior art. Furthermore, an energy-saving, rapid and environmentally mild coating process is required, in order to be able to coat even large surfaces economically. A further requirement is that it should be possible to form the coated objects without impairing the coating. The object, therefore, was to provide for these purposes a solvent-free, thin coating system having a high scratch resistance and chemical resistance to alkaline and acidic cleaning agents, such as are used in households and in commerce or in the food-processing industry.
  • this object is achieved by the provision of a solvent-free liquid coating material which is cross-linked by means of high-energy radiation and, within a temperature range of 0 to 90° C., preferably 15 to 70° C., has a viscosity of less than 1000 mPas, containing
  • the coating material according to the invention is used preferably as coating material for metallic surfaces having thin coatings which are resistant to hydrolysis and to cleaning agents and are scratch resistant.
  • the invention also provides the use of the coating material according to the invention, where the coating material is rendered antibacterial.
  • the invention also provides a process for coating metallic surfaces, wherein the substrate is optionally first of all cleaned and degreased, the coating material according to the invention is then applied in a layer thickness of 0.5 to 20 ⁇ m and finally the coating is cross-linked by means of high-energy radiation.
  • the invention further provides a process for coating those surfaces wherein, prior to the cross-linking step, the coated surface is provided with a removable protective coating film.
  • the process according to the invention and the coating material according to the invention are particularly suitable for use on surfaces consisting of ferrous materials, steel and alloyed steel, light metals such as aluminum, magnesium, titanium, non-ferrous metals such as copper, zinc, tin, or precious metals such as gold, silver or alloys thereof.
  • This surface may be ground, brushed, polished, electrochemically treated or electrolytically coated, for example, cadmium-plated, chromium-plated or nickel-plated.
  • Metallized plastics surfaces are also suitable.
  • the substrate may have any shape, but is preferably in the form of sheets, strips or rolls.
  • the coating materials according to the invention contain polymerizable oligomers containing unsaturated double bonds such as, for example, polyester oligomers or polyether oligomers having lateral or terminal (meth)acrylic groups, or preferably (meth)acrylate functional aliphatic, cycloaliphatic and/or aromatic epoxide compounds or polyurethane oligomers having reactive (meth)acrylate groups.
  • These oligomers are to have at least two functional unsaturated double bonds and in general have a molecular weight of between 500 and 15000. They are obtainable commercially.
  • the quantity is 40 to 90 wt. %, in particular 45 to 85 wt. %, and mixtures of different oligomers are also possible.
  • the coating material is also to contain at least one mono-, di-, tri- or polyfunctional unsaturated low-molecular (meth)acrylate, with separate compounds or mixtures possibly being present.
  • examples of such compounds are: optionally alkoxylated alkanediol (meth)acrylates or alkanetriol (meth)acrylates, such as 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trialkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, tetraalkylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerol alkoxytri(meth)acrylate, alkoxylated neopentyl glycol di(meth)acrylate; (meth)acrylic epoxide compounds, such
  • (meth)acrylates are examples of monofunctional acrylate compounds which can be used: linear, branched or cyclic alkyl (meth)acrylates, such as n-/isoalkyl (meth)acrylate, cyclohexyl (meth)acrylate,
  • a proportion of vinyl ethers may also be used, for example, vinyl ethyl ether, vinyl propyl ether, vinyl isobutyl ether, vinyl dodecyl ether, butanediol-1,4-divinyl ether, diethylene glycol divinyl ether, hydroxybutyl vinyl ether.
  • the monomeric acrylate compounds may be present separately or as a mixture, the total quantity amounting to between 5 and 60 wt. %, in particular between 15 and 50 wt. %.
  • the coating materials may also contain di- or trialkoxysilanes having additional organofunctional groups.
  • these are aminopropyltrialkoxysilane, bis(trialkoxysilylpropyl)amine, hydroxyethyl-trialkoxysilane, carboxypropyltrialkoxysilane, vinyltrialkoxysilane, with alkoxy in each case denoting methoxy, ethoxy, propoxy or butoxy.
  • the quantity is to be preferably between 0 and 15 wt. %.
  • the coating materials are to contain methacrylate compounds which have acidic groups and contain one, two or more (meth)acrylic groups and in addition acidic functional groups.
  • the quantity of this component is to be between 0.1 and 20 wt. %, preferably between 0.5 and 10 wt. %.
  • acidic functional groups are carboxyl groups, phosphoric or phosphonic groups, sulfo groups and derivatives thereof, for example, esters. Phosphoric groups are particularly preferred.
  • the known, preferably radical, initiators can be used as photoinitiators, such as, for example, 2-benzyldimethylamino-1-(4-morpholinophenyl)butanone-1, benzil dimethylketal or dimethoxyphenylacetophenone, ⁇ -hydroxybenzyl phenyl ketone, 1-hydroxy-l-methylethyl phenyl ketone, oligo-2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone, benzophenone, methylorthobenzoyl benzoate, methyl benzoyl formate, 2,2-diethoxyacetophenone, 2,2-di-sec.-butoxyacetophenone, p-phenylbenzophenone, 2-isopropylthioxanthone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 1,2-benzanthraquinone
  • the coating material according to the invention contains small quantities of other additives which have a beneficial influence on, for example, the flow properties, film formation, adhesion or resistance of the coating material.
  • these are flow-control agents, such as fluorinated polysilicone glycols, silicone glycols, polyether polysiloxane copolymers.
  • the known agents based on sterically hindered amino compounds can be used as light stabilizers.
  • the coating material may also contain dyes, optical brighteners and/or pigments as additives.
  • Dyes are those based on organic dyes, which are soluble in the coating material. These form colored transparent coatings after the film has cured, and together with the substrate surface can produce special visual effects.
  • Optical brighteners are compounds of the type which absorb UV radiation and reradiate it in visible light; they may, for example, be selected from among the triazine derivatives.
  • pigments are meant organic or inorganic, colored or uncolored pigment preparations, such as iron oxide pigments, titanium dioxide pigments, carbon black, quinacridone or phthalocyanine pigments. These have to be homogeneously distributed in the coating material.
  • the particle size has to be appreciably less than the intended layer thickness, preferably less than 1 ⁇ m. It may be advantageous to disperse these components in portions of the liquid acrylate compounds prior to addition to the coating material.
  • Micronised fillers such as, for example, silica, aluminum oxide, titanium dioxide or barium sulfate, may also be used. These are white, colorless or opaque/transparent and are used in finely dispersed form. Depending on quantity and type, they can influence the surface hardness, structure and scratch resistance of the coating.
  • the quantity of auxiliary substances is to be between 0.1 and 20 wt. %, preferably 0.5 to 15 wt. %.
  • the coating material may contain antibacterial or biocidal compounds.
  • antibacterial or biocidal compounds are, for example, organic substances, such as bioguanidines, substituted benzalkonium halides, alkyl polyvinylpyridines, betaine, or inorganic compounds, such as silver salts or finely divided silver particles within the particle-size range of a few nm.
  • the quantity is to be 0.1 to 5 wt. % and depends on the activity of the substance used. These compounds are incorporated into the coating material and are not destroyed during the cross-linking reaction. They result in surfaces having long-term antibacterial action.
  • the components of the coating material according to the invention can be mixed together by means of known methods.
  • it may be useful to dissolve or, for example, in the case of pigments, to disperse solid components in components of low viscosity.
  • it may be beneficial to premix these in components of low viscosity prior to addition to the coating material and limit a possible reaction.
  • the process according to the invention can be adapted for the objects to be coated in the process.
  • the substrate is subjected to a cleaning step, which can be carried out by dipping, spraying, high-pressure or injection spraying or with the assistance of ultrasound or electrolysis.
  • a cleaning step which can be carried out by dipping, spraying, high-pressure or injection spraying or with the assistance of ultrasound or electrolysis.
  • dust particles, oxide layers, adhering residues or fatty/oily substances are removed from the production process.
  • the known, preferably aqueous, cleaning agents can be used for the cleaning process.
  • the surface is rinsed with water, dried and then immediately further processed.
  • no further pretreatment is carried out prior to the coating with the coating material according to the invention; in particular, no primer is applied.
  • the substrate can be covered with the coating material by means of the known methods of application.
  • the spraying systems commonly used in coating technology such as, for example, airless, air-assisted or electrostatically assisted spraying processes, are suitable, or even manual application by brush.
  • the coating material is applied to a level surface of a workpiece or of a metal strip by flooding/squeezing off, spraying/squeezing off, or by suitable squeegee or roller applications.
  • the viscosity of the coating material during the application is to be below 1000 mPas, preferably below 300 mPas (measured in a cone/plate viscometer).
  • the layer thickness of the coating material is generally 0.5 to 20 ⁇ m, in particular 1 to 10 ⁇ m, particularly preferably up to 5 ⁇ m.
  • the coating material is generally applied at temperatures of between 0° C. and 90° C., preferably 15° C. and 70° C.
  • the coating is then cross-linked by high-energy radiation such as, for example, UV radiation, electron radiation or ⁇ -radiation.
  • the electron radiation should have energy values of between 150 and 350 keV.
  • cross-linking is effected by UV radiation, in particular having a wavelength of 150 to 800 nm, particularly preferably of between 200 and 450 nm.
  • Suitable radiation sources are known to the person skilled in the art.
  • the intensity of radiation and the duration of the radiation depend on the processing conditions, for example, distance of the radiation source or relative movement between source and substrate. The duration, however, is generally below 60 seconds, preferably between 0.001 and 30 seconds.
  • the respective variables for the equipment can be determined by the person skilled in the art by simple adjustment.
  • the oxygen content may be decreased in the zone above the substrate to be cross-linked.
  • it is to be in particular below 3000 ppm, preferably below 1000 ppm.
  • This can be effected, for example, by partial or complete exchange of the ambient air present in the cross-linking zone for inert gases, for example, argon, nitrogen, CO 2 or mixtures of these.
  • inert gases for example, argon, nitrogen, CO 2 or mixtures of these.
  • Another embodiment of the invention includes the additional step wherein, after the application of the coating material, a film which is permeable to the high-energy radiation used is first of all applied to the substrate. It is possible to apply such a film to three-dimensional substrates, but it is preferred that the substrate be a sheet or strip.
  • the application is carried out preferably by a mechanical method; for example, the tear-resistant film can be withdrawn from a delivery roll and applied, free from voids, to the substrate surface by means of a roller.
  • the coating material under the film is cross-linked by radiation.
  • the film consists, for example, of polyethylene, polypropylene, PET or mixtures of these. It is colored or, preferably, transparent. The film must not react with the coating material. It is tear-resistant, so that in a subsequent processing step it can be removed from the substrate surface by drawing off. This can also be done at the premises of the end-user, so that the film can serve as protection for the object during further processing and/or transport.
  • the use of the coating material according to the invention results in coated substrates, in particular of the metallic type, having a thin surface coating.
  • special visual effects can be achieved such as, for example, metallic lustre, dulling, structures or colorations.
  • Preferred uses of the objects coated according to the invention are metal sheets, metal parts or profiled metals used in architecture, for interior fittings of buildings or in furniture-making, as well as metallic ornaments.
  • the metallic workpieces coated according to the invention can be used in the manufacture of machines, articles or equipment for households, sanitary applications, hospitals as well as for the food-processing or pharmaceutical industries. For the last-named fields, mainly high-grade steel is used.
  • the coatings according to the invention exhibit good stability and resistance to soiling by a multitude of agents of the type found, for example, in households or in the food industry, such as black tea, black ink, condensed milk, fruit juices, vinegar, mustard, ketchup, mayonnaise, onions, sugar and caramel.
  • agents of the type found, for example, in households or in the food industry, such as black tea, black ink, condensed milk, fruit juices, vinegar, mustard, ketchup, mayonnaise, onions, sugar and caramel.
  • the fingerprints which are left on uncoated metal surfaces do not leave any permanent traces on metal coated according to the invention, and can be easily removed.
  • the coatings are also resistant to acidic and alkaline cleaning agents such as, for example, rinsing agents, so-called “steel gloss” or all-purpose cleaning agents.
  • the visual appearance of the surface is completely preserved.
  • brushed sheets of high-grade steel were used for Examples 1 to 9.
  • All substrates Prior to being coated, all substrates were degreased by means of an aqueous, slightly alkaline cleaning agent and then dried.
  • the components of the coating material according to the invention were homogenised by intensive mixing in high-speed stirrers.
  • the coating material was applied in a layer weight of ⁇ 5 g/m 2 by means of a roll coater or coating knife and cured in a standard atmosphere by means of UV radiation (emitter type: Fusion VPS/1 600, H-emitter, 240 W/cm, 100% performance) in a UV unit with a conveyor belt speed of 20 m/min.
  • Example 9 Substrate Layer Cleaning Finger- Example (brushed) thickness Appearance agent print 10 brass 5 ⁇ m in order + + (MS 39) 11 AlMg1 5 ⁇ m in order + + 12 copper 5 ⁇ m in order 0 +

Abstract

Process for the production on metal or plastic surfaces of thin, hydrolysis-resistant, scratch-resistant and stain-resistant coatings, wherein the coating material can be applied directly to the cleaned metal surface and subsequently cross-linked by high-energy radiation, in particular UV radiation. The substrates can be coated in the form of strip and only subsequently brought into the required external shape. Coated substrates such as these are no longer susceptible to staining by food, cleaning agents or fingerprints and can also be rendered antibacterial. Objects coated in this manner are thus suitable for use in architecture, for interior fittings of buildings, in furniture-making as well as for ornamental applications, and in particular in households, in sanitary applications, in hospitals and in the food-processing and pharmaceutical industries.

Description

    CROSS-REFERENCE
  • This application is a divisional of U.S. application Ser. No. 10/796,681, filed 9 Mar., 2004, which is a continuation under 35 USC Sections 365(c) and 120 of International Application No. PCT/EP02/09967, filed 6 Sep. 2002 and published 20 Mar. 2003 as WO 03/022945, which claims priority from German Application No. 10144531.8, filed 11 Sep. 2001, each of which is incorporated herein by reference in its entirety.
    • FIELD OF THE INVENTION
  • The present invention relates to a process for producing stain-resistant function coatings for metal surfaces, in particular aluminum or high-grade steel surfaces, as well as suitable coating materials for these.
    • DISCUSSION OF THE RELATED ART
  • A multitude of appliances, equipment and machines made of metal, in particular high-grade steel or aluminum, are used in households, in sanitary applications, in hospitals as well as in the food-processing and pharmaceutical industries. Here, owing to its high resistance to corrosion, e.g. high-grade steel is preferably used. This is frequently used with a polished or brushed surface and without additional coatings. Furthermore, a multitude of metallic parts having very different compositions are also used in architecture, for interior fittings of buildings, in furniture-making as well as for ornamental applications. In these cases, too, the surface of the metal is frequently polished, brushed or otherwise provided with surface patterns and is used without the application of further coatings.
  • In this form, the metal surface is highly susceptible to soiling by dust, food or cleaning agents, or marking by fingerprints. A number of methods of treating the surfaces of metals in order to improve the scratch resistance of the surface or to avoid soiling have already been proposed. These involve coating processes using solvent-based and aqueous systems, for example, aqueous electrophoretically precipitable dip coatings, or powder coatings. These coatings are intended to improve the soiling behavior and the scratch resistance of the surface. Disadvantages of the processes are, for example, the curing conditions, such as time, temperature, as well as the consequent plant dimensions. Moreover, it is frequently impossible to form the objects without destroying the surface coating.
  • DE 199 57 325 and DE 199 52 323 describe coating materials for metals or plastics; there the coating materials are heat-curable and based on aqueous sols consisting of organosilicon compounds. EP 1 036 829 deals with UV-cross-linkable coating materials for metals and conductive plastics, but describes only aqueous systems, which are applied to electrically conducting substrates by means of electrophoretic coating and are subsequently first of all dried at elevated temperature, then post-cured under UV light.
  • JP-A-07/171496 and JP-A-04/150976 (1992) describe heat-curable coatings on high-grade steel which are produced from polyester resins and silicate resin or melamine resin. JP 10/228446 and EP 0 789 065 describe special UV-cross-linking coating systems substantially for coating wood, which are applied in layers of above 20 or 30 μm.
  • Although, therefore, there exists an extensive prior art concerning UV-cross-linking coating materials, the problem of coating with thin layer thicknesses in order to avoid soiling of metal or even of plastics substrates has not yet been solved. In this connection, the coated surface should have a good stain resistance and be scratch resistant; in addition, the natural appearance in particular of brushed or otherwise structured metal surfaces should be preserved. No observations about these requirements are made in prior art. Furthermore, an energy-saving, rapid and environmentally mild coating process is required, in order to be able to coat even large surfaces economically. A further requirement is that it should be possible to form the coated objects without impairing the coating. The object, therefore, was to provide for these purposes a solvent-free, thin coating system having a high scratch resistance and chemical resistance to alkaline and acidic cleaning agents, such as are used in households and in commerce or in the food-processing industry.
    • BRIEF SUMMARY OF THE INVENTION
  • According to the invention, this object is achieved by the provision of a solvent-free liquid coating material which is cross-linked by means of high-energy radiation and, within a temperature range of 0 to 90° C., preferably 15 to 70° C., has a viscosity of less than 1000 mPas, containing
      • a) 40 to 90 wt. % of at least one oligomeric, linear or branched epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate and/or urethane (meth)acrylate,
      • b) 5 to 60 wt. %, preferably 10 to 60 wt. %, of at least one monofunctional liquid (meth)acrylate or di-, tri- or poly(meth)acrylate compound, and
      • c) 0.1 to 20 wt. % of methacrylate compounds containing acidic groups,
      • d) optionally 0 to 30 wt. % of a di- or trialkoxysilane containing further functional groups,
      • e) 0.1 to 20 wt. % of auxiliary substances used in coating technology, such as adhesion promoters, flow-control agents, defoaming agents and/or light stabilizers as well as photoinitiators.
  • The coating material according to the invention is used preferably as coating material for metallic surfaces having thin coatings which are resistant to hydrolysis and to cleaning agents and are scratch resistant. The invention also provides the use of the coating material according to the invention, where the coating material is rendered antibacterial.
  • The invention also provides a process for coating metallic surfaces, wherein the substrate is optionally first of all cleaned and degreased, the coating material according to the invention is then applied in a layer thickness of 0.5 to 20 μm and finally the coating is cross-linked by means of high-energy radiation. The invention further provides a process for coating those surfaces wherein, prior to the cross-linking step, the coated surface is provided with a removable protective coating film.
    • DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS OF THE INVENTION
  • The process according to the invention and the coating material according to the invention are particularly suitable for use on surfaces consisting of ferrous materials, steel and alloyed steel, light metals such as aluminum, magnesium, titanium, non-ferrous metals such as copper, zinc, tin, or precious metals such as gold, silver or alloys thereof. This surface may be ground, brushed, polished, electrochemically treated or electrolytically coated, for example, cadmium-plated, chromium-plated or nickel-plated. Metallized plastics surfaces are also suitable. The substrate may have any shape, but is preferably in the form of sheets, strips or rolls.
  • The coating materials according to the invention contain polymerizable oligomers containing unsaturated double bonds such as, for example, polyester oligomers or polyether oligomers having lateral or terminal (meth)acrylic groups, or preferably (meth)acrylate functional aliphatic, cycloaliphatic and/or aromatic epoxide compounds or polyurethane oligomers having reactive (meth)acrylate groups. These oligomers are to have at least two functional unsaturated double bonds and in general have a molecular weight of between 500 and 15000. They are obtainable commercially. The quantity is 40 to 90 wt. %, in particular 45 to 85 wt. %, and mixtures of different oligomers are also possible.
  • The coating material is also to contain at least one mono-, di-, tri- or polyfunctional unsaturated low-molecular (meth)acrylate, with separate compounds or mixtures possibly being present. Examples of such compounds are: optionally alkoxylated alkanediol (meth)acrylates or alkanetriol (meth)acrylates, such as 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trialkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, tetraalkylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerol alkoxytri(meth)acrylate, alkoxylated neopentyl glycol di(meth)acrylate; (meth)acrylic epoxide compounds, such as bisphenol A epoxide di(meth)acrylate; polyhydroxy (meth)acrylates, such as pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trisalkoxy-trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, tris(2-hydroxyalkyl) isocyanurate tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, with alkylene denoting ethylene, propylene or butylene and alkoxy denoting ethoxy, 1,2-or 1,3-propoxy or 1,4-butoxy.
  • The following (meth)acrylates are examples of monofunctional acrylate compounds which can be used: linear, branched or cyclic alkyl (meth)acrylates, such as n-/isoalkyl (meth)acrylate, cyclohexyl (meth)acrylate,
  • 4-tert.-butyl cyclohexyl (meth)acrylate, dihydrocyclopentadienyl (meth)acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth)acrylate, allyl (meth)acrylate, mono(meth)acryloyl alkyl phthalate, succinate or maleate; alkanediol mono(meth)acrylates, such as hydroxypropyl (meth)acrylate, polyalkylene glycol (meth)acrylate, monoalkoxytrialkylene glycol (meth)acrylate, 2,3-epoxypropyl (meth)acrylate; aromatic (meth)acrylates, such as nonylphenol (meth)acrylate,2-phenoxyalkyl (meth)acrylate; acrylamides, such as N,N-dialkyl (meth)acrylamide, N,N-dialkylaminoalkyl (meth)acrylamide. A proportion of vinyl ethers may also be used, for example, vinyl ethyl ether, vinyl propyl ether, vinyl isobutyl ether, vinyl dodecyl ether, butanediol-1,4-divinyl ether, diethylene glycol divinyl ether, hydroxybutyl vinyl ether. The monomeric acrylate compounds may be present separately or as a mixture, the total quantity amounting to between 5 and 60 wt. %, in particular between 15 and 50 wt. %.
  • The coating materials may also contain di- or trialkoxysilanes having additional organofunctional groups. Examples of these are aminopropyltrialkoxysilane, bis(trialkoxysilylpropyl)amine, hydroxyethyl-trialkoxysilane, carboxypropyltrialkoxysilane, vinyltrialkoxysilane, with alkoxy in each case denoting methoxy, ethoxy, propoxy or butoxy. The quantity is to be preferably between 0 and 15 wt. %.
  • Preferably, the coating materials are to contain methacrylate compounds which have acidic groups and contain one, two or more (meth)acrylic groups and in addition acidic functional groups. The quantity of this component is to be between 0.1 and 20 wt. %, preferably between 0.5 and 10 wt. %. Examples of such acidic functional groups are carboxyl groups, phosphoric or phosphonic groups, sulfo groups and derivatives thereof, for example, esters. Phosphoric groups are particularly preferred.
  • The known, preferably radical, initiators can be used as photoinitiators, such as, for example, 2-benzyldimethylamino-1-(4-morpholinophenyl)butanone-1, benzil dimethylketal or dimethoxyphenylacetophenone, α-hydroxybenzyl phenyl ketone, 1-hydroxy-l-methylethyl phenyl ketone, oligo-2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone, benzophenone, methylorthobenzoyl benzoate, methyl benzoyl formate, 2,2-diethoxyacetophenone, 2,2-di-sec.-butoxyacetophenone, p-phenylbenzophenone, 2-isopropylthioxanthone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 1,2-benzanthraquinone, benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, α-phenylbenzoin, thioxanthone, diethylthioxanthone, 1,5-acetonaphthalene, 1-hydroxycyclohexyl phenyl ketone, ethyl p-dimethylaminobenzoate. These may be used separately or as a mixture or combined with other radical initiators of the peroxide type or with amine accelerators.
  • Besides the above-mentioned binders, the coating material according to the invention contains small quantities of other additives which have a beneficial influence on, for example, the flow properties, film formation, adhesion or resistance of the coating material. Examples of these are flow-control agents, such as fluorinated polysilicone glycols, silicone glycols, polyether polysiloxane copolymers. The known agents based on sterically hindered amino compounds can be used as light stabilizers.
  • The coating material may also contain dyes, optical brighteners and/or pigments as additives. Dyes are those based on organic dyes, which are soluble in the coating material. These form colored transparent coatings after the film has cured, and together with the substrate surface can produce special visual effects. Optical brighteners are compounds of the type which absorb UV radiation and reradiate it in visible light; they may, for example, be selected from among the triazine derivatives. By pigments are meant organic or inorganic, colored or uncolored pigment preparations, such as iron oxide pigments, titanium dioxide pigments, carbon black, quinacridone or phthalocyanine pigments. These have to be homogeneously distributed in the coating material. In this connection, the particle size has to be appreciably less than the intended layer thickness, preferably less than 1 μm. It may be advantageous to disperse these components in portions of the liquid acrylate compounds prior to addition to the coating material.
  • Micronised fillers such as, for example, silica, aluminum oxide, titanium dioxide or barium sulfate, may also be used. These are white, colorless or opaque/transparent and are used in finely dispersed form. Depending on quantity and type, they can influence the surface hardness, structure and scratch resistance of the coating. The quantity of auxiliary substances is to be between 0.1 and 20 wt. %, preferably 0.5 to 15 wt. %.
  • Moreover, in a preferred embodiment the coating material may contain antibacterial or biocidal compounds. These are, for example, organic substances, such as bioguanidines, substituted benzalkonium halides, alkyl polyvinylpyridines, betaine, or inorganic compounds, such as silver salts or finely divided silver particles within the particle-size range of a few nm. The quantity is to be 0.1 to 5 wt. % and depends on the activity of the substance used. These compounds are incorporated into the coating material and are not destroyed during the cross-linking reaction. They result in surfaces having long-term antibacterial action.
  • The components of the coating material according to the invention can be mixed together by means of known methods. Here, it may be useful to dissolve or, for example, in the case of pigments, to disperse solid components in components of low viscosity. To ensure stability in storage, in the case of particularly reactive components it may be beneficial to premix these in components of low viscosity prior to addition to the coating material and limit a possible reaction.
  • The process according to the invention can be adapted for the objects to be coated in the process. Depending on the condition of its processing, the substrate is subjected to a cleaning step, which can be carried out by dipping, spraying, high-pressure or injection spraying or with the assistance of ultrasound or electrolysis. In the course of this, dust particles, oxide layers, adhering residues or fatty/oily substances are removed from the production process. The known, preferably aqueous, cleaning agents can be used for the cleaning process. After the cleaning process, the surface is rinsed with water, dried and then immediately further processed. Preferably, no further pretreatment is carried out prior to the coating with the coating material according to the invention; in particular, no primer is applied.
  • The substrate can be covered with the coating material by means of the known methods of application. If formed or profiled parts are to be coated, mainly the spraying systems commonly used in coating technology, such as, for example, airless, air-assisted or electrostatically assisted spraying processes, are suitable, or even manual application by brush. Particularly preferably, the coating material is applied to a level surface of a workpiece or of a metal strip by flooding/squeezing off, spraying/squeezing off, or by suitable squeegee or roller applications. Here, the viscosity of the coating material during the application is to be below 1000 mPas, preferably below 300 mPas (measured in a cone/plate viscometer).
  • The layer thickness of the coating material is generally 0.5 to 20 μm, in particular 1 to 10 μm, particularly preferably up to 5 μm.
  • The coating material is generally applied at temperatures of between 0° C. and 90° C., preferably 15° C. and 70° C. The coating is then cross-linked by high-energy radiation such as, for example, UV radiation, electron radiation or Υ-radiation. The electron radiation should have energy values of between 150 and 350 keV. Preferably, cross-linking is effected by UV radiation, in particular having a wavelength of 150 to 800 nm, particularly preferably of between 200 and 450 nm. Suitable radiation sources are known to the person skilled in the art. The intensity of radiation and the duration of the radiation depend on the processing conditions, for example, distance of the radiation source or relative movement between source and substrate. The duration, however, is generally below 60 seconds, preferably between 0.001 and 30 seconds. The respective variables for the equipment can be determined by the person skilled in the art by simple adjustment.
  • In a particular embodiment of the process, the oxygen content may be decreased in the zone above the substrate to be cross-linked. Here, it is to be in particular below 3000 ppm, preferably below 1000 ppm. This can be effected, for example, by partial or complete exchange of the ambient air present in the cross-linking zone for inert gases, for example, argon, nitrogen, CO2 or mixtures of these. An advantage of this embodiment of the process is that the required concentration of photoinitiator in the coating material can be decreased.
  • Another embodiment of the invention includes the additional step wherein, after the application of the coating material, a film which is permeable to the high-energy radiation used is first of all applied to the substrate. It is possible to apply such a film to three-dimensional substrates, but it is preferred that the substrate be a sheet or strip. The application is carried out preferably by a mechanical method; for example, the tear-resistant film can be withdrawn from a delivery roll and applied, free from voids, to the substrate surface by means of a roller. After this processing step, the coating material under the film is cross-linked by radiation. An advantage of this process is that the curing takes place underneath the film under inert conditions, i.e. in particular with the exclusion of oxygen.
  • The film consists, for example, of polyethylene, polypropylene, PET or mixtures of these. It is colored or, preferably, transparent. The film must not react with the coating material. It is tear-resistant, so that in a subsequent processing step it can be removed from the substrate surface by drawing off. This can also be done at the premises of the end-user, so that the film can serve as protection for the object during further processing and/or transport.
  • The use of the coating material according to the invention results in coated substrates, in particular of the metallic type, having a thin surface coating. At the same time, special visual effects can be achieved such as, for example, metallic lustre, dulling, structures or colorations. Preferred uses of the objects coated according to the invention are metal sheets, metal parts or profiled metals used in architecture, for interior fittings of buildings or in furniture-making, as well as metallic ornaments. In particular, the metallic workpieces coated according to the invention can be used in the manufacture of machines, articles or equipment for households, sanitary applications, hospitals as well as for the food-processing or pharmaceutical industries. For the last-named fields, mainly high-grade steel is used.
  • The coatings according to the invention exhibit good stability and resistance to soiling by a multitude of agents of the type found, for example, in households or in the food industry, such as black tea, black ink, condensed milk, fruit juices, vinegar, mustard, ketchup, mayonnaise, onions, sugar and caramel. The fingerprints which are left on uncoated metal surfaces do not leave any permanent traces on metal coated according to the invention, and can be easily removed. In particular, at temperatures of up to 60° C. the coatings are also resistant to acidic and alkaline cleaning agents such as, for example, rinsing agents, so-called “steel gloss” or all-purpose cleaning agents. At the same time, the visual appearance of the surface is completely preserved.
  • The invention is explained in more detail by means of the following Examples, but the selection of the Examples does not constitute a limitation to the scope of the invention. Unless otherwise specified, all quantitative data in the following Examples are per cent by weight or parts by weight, based on the total composition.
    • EXAMPLES
  • In the following coatings according to the present invention, brushed sheets of high-grade steel were used for Examples 1 to 9. Prior to being coated, all substrates were degreased by means of an aqueous, slightly alkaline cleaning agent and then dried. The components of the coating material according to the invention were homogenised by intensive mixing in high-speed stirrers. The coating material was applied in a layer weight of<5 g/m2 by means of a roll coater or coating knife and cured in a standard atmosphere by means of UV radiation (emitter type: Fusion VPS/1 600, H-emitter, 240 W/cm, 100% performance) in a UV unit with a conveyor belt speed of 20 m/min.
  • The individual Examples and results are shown in Tables 1 and 2 below (quantities in parts by weight).
    TABLE 1
    Example/RawMaterial 1 2 3 4 5 6 7 8 9
    1 Aliphatic epoxy acrylate 61.9 — — — — — — — —
    2 Aliphatic hexa-functional — 56.9 56.9  56.9 — 34.0  56.9  31.5  31.6 
    urethane acrylate Mw 1000
    3 Aromatic epoxy — — — — 80.8  37.0  — 34.3  34.5 
    diacrylate Mw 460
    4 Isobornyl acrylate 30.6 35.1 35.1  35.1 — 21.1  35.1  19.4  19.5 
    5 Neopentyl glycol propoxylate 20.0 20.0 — — 10.0  2.1 — 2.0 2.0
    diacrylate
    6 Vinyltrimethoxy- — — 5.0 15.0 — — 5.0 — —
    silane
    7 Bis(gamma-trimethoxysilylpropyl) 10.0 10.0 — — 4.2 1.0 — 0.9 0.8
    amine
    8 Acid triacrylate  2.5  3.0 3.0  3.0 — 1.8 3.0 1.7 1.7
    (acid value 150)
    9 Phosphoric acid acrylate (acid — — — 3.0 — — 2.8 2.8
    value 300)
    10 Photoinitiator  5.0  5.0 5.0  5.0 5.0 3.0 4.5 4.6 4.7
    11 Commercial biocide — — — — — — 0.5 — —
    12 Hydrophobic silica — — — — — — — 2.8 —
    13 Nanoparticulate Al2O3 2.4

    Photoinitiator is in the form of a 1.5:1 mixture of 1-hydroxy-1-methylethyl phenyl ketone and 1-hydroxycyclohexyl phenyl ketone.

    Methods of measurement:
    • 1. Fingerprint: a fingerprint was made on the coated metal sheet and assessed visually. It was optionally wiped off with a soft, dry cloth.
    • 2. Cross cut in accordance with DIN 53151: cross cuts were made using a cross-hatch cutter (Erichsen Model 295) and glued over with an adhesive tape, which was then torn off and the cuts assessed. The gluing and tearing off were again carried out similarly after the cut had been exposed to steam. The cross cut test results are reported on a scale of from 0 (no additional damage except the cuts) to 5 (large sections of the coating removed from the surface).
    • 3. Soiling: a 5 cm2 area of the surface of the coated metal sheet was covered with the test agents (black tea, lemon juice, mustard, ketchup, mayonnaise) and stored for 1 hour at 6° C. The metal sheet was then rinsed with water and dried with a soft cloth.
    • 4. Solvent resistance: a few drops of solvent were applied to the coated metal sheet and, after about 5 seconds, removed with a soft cloth. The swelling and dissolving behavior of the coating were assessed.
    • 5. Steam test: The metal sheet bent by 90° was positioned at a small distance above a vessel filled with boiling water and there exposed to steam for 2 hours.
  • The results of the examinations of the surface quality and of the resistance of the coatings according to the invention are summarized in Table 2 below. The surface qualities and the scratch resistance are good; the sensitivity to fingerprints is likewise good in all the coatings according to the invention.
  • In the following tables, a “+” signifies that a positive or favorable result was obtained while “0” means that an intermediate (medium) result was obtained. A negative or unfavorable result (none of which were obtained in the testing reported herein) would be signified by a “−” sign.
    TABLE 2
    Resistance to
    Surface quality Mild Strong
    Finger- Scratch cleaning cleaning
    Example Prints1 Resistance6 Crosscut2 Foods3 agents3 agents7 Slovent4 Steam5
    1 + + 0(0) 0 0 + not +
    determined
    2 0 + 0(0) + + + not +
    determined
    3 + + 0(0) + + + not 0
    determined
    4 + + 0(0) + + 0 + 0
    5 + + 0(0) + + + + +
    6 + + 0(1) + + + + +
    7 + + 0(0) + + + + 0
    8 + + 0(0) + + + + +
    9 + + 0(0) + + + + +

    1Visual assessment of fingerprints

    2Marking in accordance with DIN 53151; results after exposure to steam are shown in brackets.

    3Foods: mustard, tea, mayonnaise, ketchup, lemon juice, et cetera; mild cleaning agents: all-purpose cleaning agents, rinsing agents, et cetera

    4The tests were carried out using acetone, naphtha and ethanol.

    5Sample metal sheets bent by 90° were treated with steam for 2 h and assessed visually.

    6Determined using a hardness test rod 318, Erichsen

    7Cleaning agents: oven cleaner, Ceran cleaner etc.
    • Examples 10-12
  • Additional substrates were coated and tested using the coating material from Example 9:
    Substrate Layer Cleaning Finger-
    Example (brushed) thickness Appearance agent print
    10 brass 5 μm in order + +
    (MS 39)
    11 AlMg1 5 μm in order + +
    12 copper 5 μm in order 0 +

Claims (20)

1. A process for applying a fingerprint resistant coating on a metal surface, said process comprising:
applying to a metal surface a layer of coating material, comprising:
a. 40 to 90 wt. % of at least one oligomeric substance selected from the group consisting of epoxy (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, and polyurethane (meth)acrylates, wherein said oligomeric substance is linear or branched and contains at least two unsaturated double bonds;
b. 5 to 60 wt. % of at least one low molecular weight (meth)acrylate selected from the group consisting of monofunctional, difunctional, trifunctional and polyfunctional (meth)acrylate compounds;
c. 0.1 to 20 wt. % of at least one (meth)acrylate compound containing one or more acidic groups; and
d. 0.1 to 20 wt. % of at least one auxiliary substance selected from the group consisting of adhesion promoters different from c, flow-control agents, defoaming agents, light stabilizers, dyes, pigments, biocides, fillers and photoinitiators;
wherein the coating material has a viscosity of less than 1000 mPas within a temperature range of 0 to 90° C.; and
crosslinking the layer of coating material by means of high-energy radiation such that a fingerprint resistant coating is formed.
2. The process according to claim 1 wherein cross-linking of said layer is by means of high-energy radiation selected from UV radiation, electron radiation or gamma-radiation.
3. The process according to claim 2 wherein the high-energy radiation used is UV radiation.
4. The process according to claim 2 wherein said layer of coating material is from 0.5 to 20 μm in thickness.
5. The process according to claim 2 wherein said layer of coating material is from 1 to 10 μm in thickness.
6. The process according to claim 2 wherein no pretreatment or primer is applied to the metal surface prior to said layer of coating material.
7. The process according to claim 2 wherein the high-energy radiation used has a wavelength of 200 to 450 nm.
8. The process according to claim 2 wherein the coating material after cross-linking is transparent.
9. The process according to claim 2 wherein said metal surface is in the form of a strip and is coated by roller application.
10. The process according to claim 2 wherein during the cross-linking step the metal surface having the layer applied thereon is in a low-oxygen or oxygen-free atmosphere.
11. The process according to claim 2 wherein after applying said layer of coating material and before cross-linking said layer a high-energy radiation permeable film is applied to said layer.
12. The process according to claim 11 wherein the film is comprised of at least one polymer selected from the group consisting of polyethylene, polypropylene, and PET and is separable from the layer after cross-linking.
13. The process according to claim 2 additionally comprising the step of forming the metal surface having the cross-linked layer thereon.
14. The process according to claim 2 wherein said metal surface is cleaned prior to applying said layer of coating material but does not have a primer or pretreatment layer applied to the metal surface.
15. A process for applying a fingerprint resistant coating on a metal surface, said process comprising:
optionally cleaning and drying a metal surface;
applying to the metal surface a layer of coating material, comprising:
a. 45 to 85 wt. % of at least one oligomeric substance having at least two unsaturated double bonds selected from the group consisting of aromatic epoxy (meth)acrylates, and optionally, polyester (meth)acrylates, polyether (meth)acrylates, and polyurethane (meth)acrylates, wherein said oligomeric substance is linear or branched;
b. 10 to 60 wt. % of at least one (meth)acrylate selected from the group consisting of monofunctional, difunctional, trifunctional and polyfunctional (meth)acrylate compounds;
c. 0.5 to 10 wt. % of at least one (meth)acrylate compound containing one or more phosphoric or carboxyl acidic functional groups;
d. 0.5 to 15 wt. % of at least one radical photoinitiator; and
e. up to 20 wt. % of at least one silane selected from the group consisting of dialkoxysilanes and trialkoxysilanes wherein said at least one silane contains an amine functional group;
wherein components a. through e. are selected and homogenized together such that the coating material has a viscosity of less than 300 mPas within a temperature range of 0 to 90° C. in the absence of solvent; and
crosslinking the layer of coating material by means of high-energy radiation such that a fingerprint resistant coating is formed.
16. An object comprising a metal substrate having a metal surface and a layer of a cross-linked coating material deposited on the metal surface by the process of claim 1, wherein said metal substrate is a sheet or strip.
17. An object having a metal surface and a layer of a cross-linked coating material up to 5 μm in thickness deposited on the metal surface by the process of claim 1.
18. The object according to claim 17 wherein said metal surface is comprised of a material selected from the group consisting of ferrous materials, steel, alloyed steel, light metals, non-ferrous metals and precious metals.
19. The object according to claim 18 additionally comprising a film comprising at least one polymer selected from the group consisting of polyethylene, polypropylene, and PET on said layer of cross-linked coating material.
20. A process for applying a fingerprint resistant coating on a metal surface, said process comprising:
optionally cleaning and drying a metal surface;
applying to the metal surface a layer of coating material, comprising:
a. 45 to 85 wt. % of at least one oligomeric substance having at least two unsaturated double bonds selected from the group consisting of epoxy (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, and polyurethane (meth)acrylates, wherein said oligomeric substance is linear or branched;
b. 10 to 60 wt. % of at least one (meth)acrylate selected from the group consisting of monofunctional, difunctional, trifunctional and polyfunctional (meth)acrylate compounds;
c. 0.5 to 10 wt. % of at least one (meth)acrylate compound containing one or more phosphoric or carboxyl acidic functional groups;
d. 0.5 to 15 wt. % of at least one radical photoinitiator; and
e. up to 20 wt. % of at least one silane selected from the group consisting of dialkoxysilanes and trialkoxysilanes wherein said at least one silane contains at least one functional group other than alkoxy groups;
wherein 2.0 to 20 wt. %, based upon total coating material, of the monofunctional, difunctional, trifunctional and polyfunctional (meth)acrylate compounds are linear or branched; and
crosslinking the layer of coating material by means of UV radiation such that a formable, fingerprint resistant coating is formed.
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US7816434B2 (en) 2010-10-19

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