EP3003581A1 - Coating of usage surfaces with plasma polymer layers under atmospheric pressure in order to improve the cleanability - Google Patents

Coating of usage surfaces with plasma polymer layers under atmospheric pressure in order to improve the cleanability

Info

Publication number
EP3003581A1
EP3003581A1 EP14721389.6A EP14721389A EP3003581A1 EP 3003581 A1 EP3003581 A1 EP 3003581A1 EP 14721389 A EP14721389 A EP 14721389A EP 3003581 A1 EP3003581 A1 EP 3003581A1
Authority
EP
European Patent Office
Prior art keywords
household
easily cleanable
glass
cleanable surfaces
applying easily
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP14721389.6A
Other languages
German (de)
French (fr)
Other versions
EP3003581B1 (en
Inventor
Frank JÖRDENS
Jürgen Salomon
Philipp Schaller
Gerhard Schmidmayer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BSH Hausgeraete GmbH
Original Assignee
BSH Hausgeraete GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BSH Hausgeraete GmbH filed Critical BSH Hausgeraete GmbH
Priority to PL14721389T priority Critical patent/PL3003581T3/en
Publication of EP3003581A1 publication Critical patent/EP3003581A1/en
Application granted granted Critical
Publication of EP3003581B1 publication Critical patent/EP3003581B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24C—DOMESTIC STOVES OR RANGES ; DETAILS OF DOMESTIC STOVES OR RANGES, OF GENERAL APPLICATION
    • F24C15/00—Details
    • F24C15/005—Coatings for ovens
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2203/00—Other substrates
    • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2203/00—Other substrates
    • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
    • B05D2203/35—Glass
    • 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
    • B05D2506/00—Halogenated polymers
    • B05D2506/10—Fluorinated polymers
    • 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
    • B05D2518/00—Other type of polymers
    • B05D2518/10—Silicon-containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • B05D5/086—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers having an anchoring layer

Definitions

  • the present invention relates to a method for depositing a plasma polymer layer on surfaces of enamel, glass, glass ceramic or metal, which is characterized in that the application of the surface coating in
  • the present invention further relates to household articles whose surface of enamel, glass, glass ceramic or metal has been coated by the aforesaid method.
  • EP 1 858 819 A1 discloses coatings using polysiloxanes enriched with radical scavengers.
  • the present invention provides a method for applying easily cleanable surfaces to household articles, which is characterized in that at least a portion of the substrate surface of the household article, e.g. consisting of glass, enamel, glass ceramic or metal, using one or more nozzle (s) and starting from one or more precursor (s) by means of a
  • Atmospheric pressure plasma a polymeric surface layer is deposited.
  • the atmospheric pressure plasma is generated in a preferred embodiment by a plasma generator with an output frequency in the range of 1 kHz to 1 MHz.
  • one or more precursor (s) is selected from the group consisting of fluorine and carbon-containing
  • the fluorine and carbon is preferably perfluorocyclobutane (PFCB) and the organosilicon compound is preferably hexamethyldisiloxane (HMDSO).
  • the layer thickness of the deposited polymeric surface layer is about 10 nm to about 10 ⁇ .
  • an adhesion promoting layer can be deposited prior to deposition of the polymeric surface layer by plasma polymerization.
  • the adhesion-promoting layer is preferably Si0 2 -containing.
  • a plurality of nozzles can be arranged in a row to form an array.
  • the present invention provides a household article which has at least one partial surface, preferably consisting of glass, enamel, glass ceramic or metal, which has been coated by means of the methods described above, the polymeric surface layer having virtually no polar groups.
  • a preferably SiO 2 -containing, adhesion-promoting layer is located between the partial surface consisting of glass, enamel, glass ceramic or metal and the polymeric surface layer.
  • the aforementioned household article is a kitchen appliance, more preferably an oven muffle.
  • the surface energy lowering coating is performed by a plasma polymerization process under atmospheric pressure conditions.
  • atmospheric pressure plasma also known as AD plasma or
  • Normal pressure plasma a plasma in which the pressure in the surrounding of the surrounding atmosphere - the so-called normal pressure - corresponds approximately.
  • the coating process according to the invention is carried out by using suitable
  • Precursors are excited in a nozzle in which an electrically excited plasma is ignited in such a way that they form a low-energy surface on the surface of the substrate (made of enamel, glass, glass-ceramic or metal).
  • a pulsed arc is generated in the plasma nozzle by means of high-voltage discharge.
  • a precursor gas which is usually passed by this discharge path, is excited and converted into the plasma state. This plasma then passes through a nozzle head onto the substrate surface to be coated.
  • High-frequency generators from the kHz range to the GHz range.
  • kHz sources i.e., plasma generators having an output frequency in the range of 1 kHz to 1 MHz are used.
  • the precursor gases used are preferably fluorine and carbon-containing compounds and / or organosilicon compounds.
  • organosilicon precursors siloxanes, such as. As hexamethyldisiloxane (HMDSO) called.
  • Fluorine and carbon containing compounds are preferably fluorocarbons, such as. B.
  • Process conditions or change of the precursor to produce a low energy surface are conditions or change of the precursor to produce a low energy surface.
  • Compounds and organosilicon precursors or hydrocarbons additional residual gases, such as noble gases (eg argon), oxygen, nitrogen, carbon dioxide,
  • the method according to the invention makes effective and, above all, possible
  • the coating thickness can be chosen depending on the desired properties and the precursor composition. In general, the
  • Single layer thickness less than 100 ⁇ , preferably about 10 nm to about 10 ⁇ .
  • the non-stick effect is further enhanced by roughening the surface prior to coating.
  • the present invention also relates to a household article, which a
  • the household article according to the present invention comprises both non-electrical kitchen appliances (such as cookware, pans, roasters), electric
  • Kitchen appliances such as blenders, ovens, grills, refrigerators or microwaves
  • other household appliances and furniture which have at least a partial surface of enamel, glass, glass ceramic or metal (such as glass doors, control panels).
  • the household article is an oven, more preferably an oven muffle.
  • the coated surface of the household article according to the invention is generally characterized by having virtually no polar groups.
  • the surface energy of the coated surface is preferably 40 mN / m or less, more preferably less than 20 mN / m.
  • the measurement of the surface energy and the determination of its polar and disperse fractions are carried out by customary methods known to the person skilled in the art (eg contact angle measurement and methods according to ZISMAN or OWEN, WENDT, RABEL & KAELBE).

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Chemical Vapour Deposition (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

The invention relates to a method for applying easily cleanable surfaces to domestic articles, said method being characterized in that a polymer surface layer is deposited by means of an atmospheric-pressure plasma onto at least part of the substrate surface of the domestic article composed of glass, enamel, glass ceramic, or metal. The invention further relates to domestic articles, the surface of which has been at least partially coated by means of the aforementioned method.

Description

BESCHICHTUNG VON GEBRAUCHSOBERFLÄCHEN MIT PLASMAPOLYMEREN SCHICHTEN UNTER ATMOSPHÄRENDRUCK ZUR VERBESSERUNG DER COATING OF USER SURFACES WITH PLASMAPOLYLIC LAYERS UNDER ATMOSPHERE PRESSURE TO IMPROVE THE
REINIGBARKEIT cleanability
Beschreibung description
Technisches Gebiet Technical area
Die vorliegende Erfindung betrifft ein Verfahren zur Abscheidung einer plasmapolymeren Schicht auf Gebrauchsoberflächen aus Emaille, Glas, Glaskeramik oder Metall, welches dadurch gekennzeichnet ist, dass die Aufbringung der Oberflächenbeschichtung im The present invention relates to a method for depositing a plasma polymer layer on surfaces of enamel, glass, glass ceramic or metal, which is characterized in that the application of the surface coating in
Atmosphärendruckplasma erfolgt. Atmospheric pressure plasma takes place.
Die vorliegende Erfindung betrifft des Weiteren Haushaltsartikel, deren Oberfläche aus Emaille, Glas, Glaskeramik oder Metall durch das vorgenannte Verfahren beschichtet wurde. The present invention further relates to household articles whose surface of enamel, glass, glass ceramic or metal has been coated by the aforesaid method.
Stand der Technik State of the art
Die Erzeugung einer Leichtreinigungsoberfläche aus Emaille, Glas, Glaskeramik oder Metall beruht auf der Absenkung ihrer Oberflächenenergie. So haben beispielsweise Gläser, Glaskeramiken und Emails aufgrund ihrer oxidischen Zusammensetzung (u. A. Si02, Al203, Na20, K20) Oberflächenenergien von mehr als 40 mN/m mit einem ausgeprägten polaren Anteil. Ein ähnliches Verhalten zeigen Metalle, da die Grenzschicht Metall - Luft immer eine Oxidschicht aufweist. Dieser polare Anteil ist für das gute Anhaften von eingebrannten Lebensmittelresten (Öle, Stärke, Zucker, ...) verantwortlich. The production of a light cleaning surface of enamel, glass, glass ceramic or metal based on the reduction of their surface energy. For example, glasses, glass ceramics and enamels have surface energies of more than 40 mN / m with a pronounced polar fraction because of their oxide composition (inter alia Si0 2 , Al 2 O 3 , Na 2 O, K 2 O ) . A similar behavior is shown by metals, since the boundary layer metal - air always has an oxide layer. This polar portion is responsible for the good adhesion of baked food residues (oils, starch, sugar, ...).
Daher wurde bisher versucht, die Oberflächenenergie durch eine Beschichtung aus der Flüssigphase zu senken und den polaren Anteil auf 0 mN/m zu verringern. Bekannt sind z.B. für Email eine Beschichtung mit Silikonpolymeren (EP 0 937 012 B1 ) oder PTFE-basierte Beschichtungen (DE 19 833 375 A1 ). In EP 1 858 819 A1 sind zudem Beschichtungen unter Verwendung von mit Radikalfängern angereicherten Polysiloxanen offenbart. Therefore, attempts have been made to reduce the surface energy by a coating from the liquid phase and to reduce the polar fraction to 0 mN / m. It is known e.g. for enamel a coating with silicone polymers (EP 0 937 012 B1) or PTFE-based coatings (DE 19 833 375 A1). In addition, EP 1 858 819 A1 discloses coatings using polysiloxanes enriched with radical scavengers.
Allgemeines Kennzeichen dieser Beschichtungen ist, dass das Beschichtungsmatenal flüssig auf das Substrat aufgebracht wird und anschließend (evtl. nach Trocknung) bei erhöhter Temperatur (ca. 150°C - 400 °C) eingebrannt werden muss, wodurch sich diese Beschichtungsverfahren als energie- und zeitaufwändig gestalten. The general characteristic of these coatings is that the Beschichtungsmatenal is applied liquid to the substrate and then (possibly after drying) at elevated Temperature (about 150 ° C - 400 ° C) must be baked, making this coating process as energy and time consuming.
Ist zudem eine Beschichtung ausgewählter Teiloberflächen gewünscht, erfordern die genannten Verfahren zwangsläufig weitere Maskier- bzw. Abklebeschritte, welche den Zeitaufwand zusätzlich erhöhen. If, in addition, a coating of selected partial surfaces is desired, the methods mentioned inevitably require further masking or masking steps, which additionally increase the expenditure of time.
Zudem sind die genannten Verfahren häufig auf die Verwendung von Lösemitteln angewiesen und somit nachteilig im Hinblick auf die Schonung der Umwelt. In addition, the methods mentioned often rely on the use of solvents and thus disadvantageous with regard to the protection of the environment.
Daher besteht Bedarf an alternativen Verfahren, die eine schnelle, saubere, Therefore, there is a need for alternative methods that can provide a fast, clean,
umweltschonende und preiswerte Beschichtung ermöglichen, die gegebenenfalls selektiv ohne zusätzliche Maskierungsschritte erfolgen kann. allow environmentally friendly and inexpensive coating, which can optionally be done selectively without additional masking steps.
Kurze Beschreibung der Erfindung Brief description of the invention
Erfindungsgemäß wird das beschriebene Verschmutzungsproblem dadurch gelöst, dass die oberflächenenergiesenkende Beschichtung auf mindestens einen Teil der Oberfläche (auch Substratoberfläche) durch einen Plasmapolymerisationsprozess unter According to the described problem of contamination is achieved in that the surface energy sinking coating on at least a portion of the surface (also substrate surface) by a plasma polymerization under
Atmosphärendruckbedingungen erhalten wird. Atmospheric pressure conditions is obtained.
Im Einzelnen stellt die vorliegende Erfindung ein Verfahren zur Aufbringung von leicht reinigbaren Oberflächen auf Haushaltsartikeln bereit, welches dadurch gekennzeichnet ist, dass auf mindestens einen Teil der Substratoberfläche des Haushaltsartikels, z.B. bestehend aus Glas, Email, Glaskeramik oder Metall, unter Verwendung einer oder mehrerer Düse(n) und ausgehend von einem oder mehreren Precursor(en) mit Hilfe eines In particular, the present invention provides a method for applying easily cleanable surfaces to household articles, which is characterized in that at least a portion of the substrate surface of the household article, e.g. consisting of glass, enamel, glass ceramic or metal, using one or more nozzle (s) and starting from one or more precursor (s) by means of a
Atmosphärendruckplasmas eine polymere Oberflächenschicht abgeschieden wird. Atmospheric pressure plasma a polymeric surface layer is deposited.
Das Atmosphärendruckplasma wird in einer bevorzugten Ausführungsform durch einen Plasmagenerator mit einer Ausgangsfrequenz im Bereich von 1 kHz bis 1 MHz erzeugt. The atmospheric pressure plasma is generated in a preferred embodiment by a plasma generator with an output frequency in the range of 1 kHz to 1 MHz.
In einer weiterhin bevorzugten Ausführungsform ist einer oder mehrere Precursor(en) ausgewählt aus der Gruppe bestehend aus Fluor und Kohlenstoff enthaltenden In a further preferred embodiment, one or more precursor (s) is selected from the group consisting of fluorine and carbon-containing
Verbindungen und/oder siliciumorganischen Verbindungen. Die Fluor und Kohlenstoff enthaltende Verbindung ist ferner vorzugsweise Perfluorocyclobutan (PFCB) und die siliciumorganische Verbindung vorzugsweise Hexamethyldisiloxan (HMDSO). Compounds and / or organosilicon compounds. The fluorine and carbon The compound containing, for example, is preferably perfluorocyclobutane (PFCB) and the organosilicon compound is preferably hexamethyldisiloxane (HMDSO).
In einer Ausführungsform beträgt die Schichtstärke der abgeschiedenen polymeren Oberflächenschicht etwa 10 nm bis etwa 10 μηη beträgt. In one embodiment, the layer thickness of the deposited polymeric surface layer is about 10 nm to about 10 μηη.
In einer Ausführungsform kann vor der Abscheidung der polymeren Oberflächenschicht mittels Plasmapolymerisation eine haftvermittelnde Schicht abgeschieden werden. In one embodiment, an adhesion promoting layer can be deposited prior to deposition of the polymeric surface layer by plasma polymerization.
Vorzugsweise ist die haftvermittelnde Schicht Si02-haltig. The adhesion-promoting layer is preferably Si0 2 -containing.
In einer bevorzugten Ausführungsform wird vor der Abscheidung der polymeren In a preferred embodiment, prior to the deposition of the polymeric
Oberflächenschicht mittels Plasmapolymerisation der Teil der Substratoberfläche angeraut. Surface layer roughened by plasma polymerization of the part of the substrate surface.
Zur großflächigen Beschichtung können in einer weiteren Ausführungsform mehrere Düsen in einer Reihe zu einem Array angeordnet werden. For large-area coating, in a further embodiment, a plurality of nozzles can be arranged in a row to form an array.
Des Weiteren stellt die vorliegende Erfindung einen Haushaltsartikel bereit, welcher zumindest eine Teiloberfläche, bevorzugt bestehend aus Glas, Email, Glaskeramik oder Metall aufweist, die mit Hilfe der vorangehend beschriebenen Verfahren beschichtet wurde, wobei die polymere Oberflächenschicht praktisch keine polaren Gruppen aufweist. Furthermore, the present invention provides a household article which has at least one partial surface, preferably consisting of glass, enamel, glass ceramic or metal, which has been coated by means of the methods described above, the polymeric surface layer having virtually no polar groups.
In einer bevorzugten Ausführungsform befindet sich zwischen der Teiloberfläche bestehend aus Glas, Email, Glaskeramik oder Metall und der polymeren Oberflächenschicht eine vorzugsweise Si02-haltige, haftvermittelnde Schicht. In a preferred embodiment, a preferably SiO 2 -containing, adhesion-promoting layer is located between the partial surface consisting of glass, enamel, glass ceramic or metal and the polymeric surface layer.
In bevorzugten Ausführungsformen ist der vorstehend genannte Haushaltsartikel ein Küchengerät, besonders bevorzugt ein Backofenmuffel. In preferred embodiments, the aforementioned household article is a kitchen appliance, more preferably an oven muffle.
Detaillierte Beschreibung der Erfindung Detailed description of the invention
Gemäß der vorliegenden Erfindung wird die oberflächenenergiesenkende Beschichtung durch einen Plasmapolymerisationsprozess unter Atmosphärendruck-bedingungen durchgeführt. Generell bezeichnet der Begriff Atmosphärendruckplasma (auch AD-Plasma oder According to the present invention, the surface energy lowering coating is performed by a plasma polymerization process under atmospheric pressure conditions. In general, the term atmospheric pressure plasma (also known as AD plasma or
Normaldruckplasma) ein Plasma, bei welchem der Druck in etwa dem der umgebenden Atmosphäre - dem sogenannten Normaldruck - entspricht. Normal pressure plasma), a plasma in which the pressure in the surrounding of the surrounding atmosphere - the so-called normal pressure - corresponds approximately.
Das erfindungsgemäße Beschichtungsverfahren wird ausgeführt, indem geeignete The coating process according to the invention is carried out by using suitable
Precursoren in einer Düse, in der ein elektrisch angeregtes Plasma gezündet wird, derart angeregt werden, dass sie auf der Oberfläche des Substrats (aus Email, Glas Glaskeramik oder Metall) eine Niederenergieoberfläche bilden. Im Einzelnen wird in der Plasmadüse mittels Hochspannungsentladung ein gepulster Lichtbogen erzeugt. Ein Precursorgas, gewöhnlich wird das an dieser Entladungsstrecke vorbeiströmt, wird angeregt und in den Plasmazustand überführt. Dieses Plasma gelangt anschließend durch einen Düsenkopf auf die zu beschichtende Substratoberfläche. Precursors are excited in a nozzle in which an electrically excited plasma is ignited in such a way that they form a low-energy surface on the surface of the substrate (made of enamel, glass, glass-ceramic or metal). In detail, a pulsed arc is generated in the plasma nozzle by means of high-voltage discharge. A precursor gas, which is usually passed by this discharge path, is excited and converted into the plasma state. This plasma then passes through a nozzle head onto the substrate surface to be coated.
Als Energiequelle für das Plasma können prinzipiell alle derzeit verfügbaren Generatoren zum Einsatz kommen. Beispielsweise können Radiofrequenz- oder In principle, all currently available generators can be used as the energy source for the plasma. For example, radio frequency or
Hochfrequenzgeneratoren verwendet werden (vom kHz-Bereich bis zum GHz-Bereich). In einer bevorzugten Ausführungsform werden kHz-Quellen (d. h. Plasmageneratoren mit einer Ausgangsfrequenz im Bereich von 1 kHz bis 1 MHz) verwendet. High-frequency generators (from the kHz range to the GHz range). In a preferred embodiment, kHz sources (i.e., plasma generators having an output frequency in the range of 1 kHz to 1 MHz) are used.
Als Precursorgase werden bevorzugt Fluor und Kohlenstoff enthaltende Verbindungen und/oder siliciumorganische Verbindungen eingesetzt. Als Beispiele für siliciumorganische Precursoren seien Siloxane, wie z. B. Hexamethyldisiloxan (HMDSO) genannt. Fluor und Kohlenstoff enthaltende Verbindungen sind vorzugsweise Fluorkohlenstoffe, wie z. B. The precursor gases used are preferably fluorine and carbon-containing compounds and / or organosilicon compounds. As examples of organosilicon precursors siloxanes, such as. As hexamethyldisiloxane (HMDSO) called. Fluorine and carbon containing compounds are preferably fluorocarbons, such as. B.
Perfluorcyclobutan (PFCB). Perfluorocyclobutane (PFCB).
Denkbar ist auch, mit diesem Verfahren zunächst eine haftvermittelnde Schicht (z. B. eine Si02-haltige Schicht) aufzubringen und im Anschluss durch Variation der It is also conceivable to initially apply an adhesion-promoting layer (for example a SiO 2 -containing layer) using this method, and subsequently to obtain it by varying the
Prozessbedingungen oder Wechsel des Precursors eine Niedrigenergieoberfläche zu erzeugen. Process conditions or change of the precursor to produce a low energy surface.
Je nach einzustellendem mechanischen Belastungsgrad der Beschichtung kann es unabhängig davon vorteilhaft sein, Fluor und Kohlenstoff enthaltende Verbindungen in Kombination mit siliciumorganischen Verbindungen oder Kohlenwasserstoffen als Depending on the mechanical stress level of the coating to be set, it may be advantageous to use compounds containing fluorine and carbon in combination with organosilicon compounds or hydrocarbons
Precursormaterial einzusetzen. Im Prozess gestaltet sich dies derart aus, dass entweder Mehrschichtaufbauten realisiert werden oder durch kontinuierliche Veränderungen der Precursorgasanteile Use precursor material. In the process, this is done in such a way that either multilayer structures are realized or by continuous changes of the Precursorgasanteile
Gradientenschichten abgeschieden werden, die substratseitig sehr hart und Gradient layers are deposited, the substrate side very hard and
widerstandsfähig sind und in Richtung Außenfläche immer mehr polymere und dafür schlecht anhaftende Eigenschaften aufweisen. Resistant and towards the outer surface more and more polymeric and poorly adhering properties.
Weiterhin kann das Prozessgas neben den Fluor und Kohlenstoff enthaltenden Furthermore, the process gas in addition to the fluorine and carbon-containing
Verbindungen und siliciumorganischen Precursoren oder Kohlenwasserstoffen zusätzliche Restgase, wie etwa Edelgase (z. B. Argon), Sauerstoff, Stickstoff, Kohlendioxid, Compounds and organosilicon precursors or hydrocarbons additional residual gases, such as noble gases (eg argon), oxygen, nitrogen, carbon dioxide,
Tetrachlorkohlenstoff und Gasgemische enthalten, sofern sich dies nicht nachteilig auf die Prozessführung und die resultierende Beschichtung auswirkt. Contain carbon tetrachloride and gas mixtures, provided that this does not adversely affect the process control and the resulting coating.
Somit ermöglicht das erfindungsgemäße Verfahren nicht zuletzt aufgrund der auf einfache Art und Weise erzeugbaren Schichteigenschaften eine wirksame und vor allem Thus, not least because of the layer properties which can be generated in a simple manner, the method according to the invention makes effective and, above all, possible
vergleichsweise kostengünstige und dauereffiziente Lösung der eingangs beschriebenen Probleme. relatively inexpensive and long-term solution to the problems described above.
Die Beschichtungsdicke kann in Abhängigkeit der gewünschten Eigenschaften und der Precursor-Zusammensetzung gewählt werden. Im Allgemeinen beträgt die The coating thickness can be chosen depending on the desired properties and the precursor composition. In general, the
Einzelschichtdicke weniger als 100 μηη, vorzugsweise etwa 10 nm bis etwa 10 μηη. Single layer thickness less than 100 μηη, preferably about 10 nm to about 10 μηη.
Insgesamt gelingt es mit dem vorgeschlagenen Verfahren besonders temperaturstabile, chemikalienresistente und - wenn erforderlich - transparente Antihaft-Schichten zu erzeugen. Overall, it is possible with the proposed method particularly temperature-stable, chemical-resistant and - if necessary - to produce transparent non-stick layers.
In einer bevorzugten Ausführungsform wird der Antihaft-Effekt zusätzlich verbessert, indem die Oberfläche vor der Beschichtung aufgeraut wird. Durch die anschließende In a preferred embodiment, the non-stick effect is further enhanced by roughening the surface prior to coating. By the subsequent
Niedrigenergiebeschichtung benetzt das Wasser nur die Spitzen und kann beim Ablaufen an der Oberfläche anhaftende Schmutzpartikel somit leichter mitbefördern („Lotus-Effekt"). Low-energy coating wets the water only the tips and can thus easily carry along adhering dirt particles on the surface ("lotus effect").
Da sich bei der Verwendung eines Plasmastrahls im Gegensatz zum Sprühauftrag einer Flüssigbeschichtung keinerlei Sprühnebel bilden und der Plasmastrahl somit räumlich begrenzt ist, sind auch partielle Teilbeschichtungen der Oberfläche ohne Maskieren oder Abkleben ohne weiteren Aufwand möglich. Für eine großflächige Beschichtung (z. B. eines Backrohrbodens) können auch mehrere Plasmadüsen in einer Reihe angeordnet werden. Mit diesem Array können somit auch große Flächen - z. B. durch einen Roboter - schnell und gleichmäßig beschichtet werden (siehe Abbildung 1 ). Since the use of a plasma jet in contrast to the spray application of a liquid coating form no spray and the plasma jet is thus limited in space, and partial partial coatings of the surface without masking or masking are possible without further effort. For a large-area coating (eg, a baking tube bottom), it is also possible to arrange a plurality of plasma nozzles in a row. With this array can thus also large areas -. B. by a robot - be coated quickly and evenly (see Figure 1).
Die Abscheidung der plasmapolymeren Schicht unter Atmosphärenbedingungen erfordert zudem keine Lösemittel, wodurch das erfindungsgemäße Verfahren gegenüber The deposition of the plasma polymer layer under atmospheric conditions also requires no solvents, whereby the inventive method
herkömmlichen Flüssigbeschichtungen im Hinblick auf die Umweltfreundlichkeit vorteilhaft ist. Conventional liquid coatings in terms of environmental friendliness is advantageous.
Im Vergleich zu nasschemisch aufgebrachten Oberflächen ist es mittels geeigneter Compared to wet-chemically applied surfaces, it is by means of suitable
Precursor- und Verfahrensparameter möglich, absolut unpolare Oberflächen zu erzeugen, die praktisch keine polaren Gruppen, die eine Anhaftung fördern würden, mehr aufweisen. Gemäß der vorliegenden Erfindung wird ebenfalls ein Küchengerät bereitgestellt, dessen Oberfläche zumindest teilweise nach den vorstehend beschriebenen Verfahren beschichtet wurde. Precursor and process parameters make it possible to produce absolutely nonpolar surfaces that have virtually no polar groups that would promote adhesion. According to the present invention, there is also provided a kitchen utensil whose surface has been at least partially coated by the methods described above.
Die vorliegende Erfindung betrifft zudem ein Haushaltsartikel, welches eine The present invention also relates to a household article, which a
Gebrauchsoberfläche aus Email, Glas, Glaskeramik oder Metall aufweist, welche zumindest teilweise nach den vorstehend beschriebenen Verfahren beschichtet wurde, gekennzeichnet dadurch, dass die beschichtete Oberfläche praktisch keine polaren Gruppen aufweist. User surface of enamel, glass, glass ceramic or metal, which has been coated at least partially by the methods described above, characterized in that the coated surface has virtually no polar groups.
Der Haushaltsartikel entsprechend der vorliegenden Erfindung umfasst sowohl nichtelektrische Küchengeräte (wie z. B. Kochgeschirr, Pfannen, Bräter), elektrische The household article according to the present invention comprises both non-electrical kitchen appliances (such as cookware, pans, roasters), electric
Küchengeräte (wie z. B. Mixer, Backöfen, Grillgeräte, Kühlschränke oder Mikrowellen) sowie weitere Haushaltsgeräte und -möbel, welche zumindest eine Teiloberfläche aus Email, Glas, Glaskeramik oder Metall aufweisen (wie z. B. Glastüren, Bedienungsblenden). In einer bevorzugten Ausführungsform ist der Haushaltsartikel ein Backofen, besonders bevorzugt ein Backofenmuffel. Kitchen appliances (such as blenders, ovens, grills, refrigerators or microwaves) and other household appliances and furniture, which have at least a partial surface of enamel, glass, glass ceramic or metal (such as glass doors, control panels). In a preferred embodiment, the household article is an oven, more preferably an oven muffle.
Die beschichtete Oberfläche des erfindungsgemäßen Haushaltsartikels ist generell dadurch gekennzeichnet, dass sie praktisch keine polaren Gruppen aufweist. Die Oberflächenenergie der beschichteten Oberfläche beträgt vorzugsweise 40 mN/m oder weniger, besonders bevorzugt weniger als 20 mN/m. Vorzugsweise beträgt der polare Anteil der The coated surface of the household article according to the invention is generally characterized by having virtually no polar groups. The surface energy of the coated surface is preferably 40 mN / m or less, more preferably less than 20 mN / m. Preferably, the polar portion of
Oberflächenenergie weniger als 5 mN/m, ferner bevorzugt weniger als 1 mN/m, besonders bevorzugt weniger als 0,5 mN/m, speziell bevorzugt 0 mN/m. Die Messung der Oberflächenenergie sowie die Ermittlung deren polarer und disperser Anteile erfolgen nach gängigen, dem Fachmann bekannten Verfahren (z. B. Kontaktwinkelmessung und Verfahren nach ZISMAN bzw. OWEN, WENDT, RABEL & KAELBE). Surface energy less than 5 mN / m, more preferably less than 1 mN / m, especially preferably less than 0.5 mN / m, especially preferably 0 mN / m. The measurement of the surface energy and the determination of its polar and disperse fractions are carried out by customary methods known to the person skilled in the art (eg contact angle measurement and methods according to ZISMAN or OWEN, WENDT, RABEL & KAELBE).

Claims

PATENTANSPRÜCHE
1 . Verfahren zur Aufbringung von leicht reinigbaren Oberflächen auf Haushaltsartikel, gekennzeichnet dadurch, dass auf mindestens einen Teil der Oberfläche eines 1 . Method for applying easily cleanable surfaces to household articles, characterized in that at least part of the surface of a
Haushaltsartikel, z.B. bestehend aus Glas, Email, Glaskeramik oder Metall, unter Household items, e.g. consisting of glass, enamel, glass ceramic or metal, under
Verwendung einer oder mehrerer Düse(n) und ausgehend von einem oder mehreren Precursor(en) mit Hilfe eines Atmosphärendruckplasmas eine polymere Oberflächenschicht abgeschieden wird. Using one or more nozzle (s) and starting from one or more precursor (s) by means of an atmospheric pressure plasma, a polymeric surface layer is deposited.
2. Verfahren zur Aufbringung von leicht reinigbaren Oberflächen auf Haushaltsartikeln nach Anspruch 1 , wobei das Atmosphärendruckplasma durch einen Plasmagenerator mit einer Ausgangsfrequenz im Bereich von 1 kHz bis 1 MHz erzeugt wird. 2. A method for applying easily cleanable surfaces to household articles according to claim 1, wherein the atmospheric pressure plasma is generated by a plasma generator with an output frequency in the range of 1 kHz to 1 MHz.
3. Verfahren zur Aufbringung von leicht reinigbaren Oberflächen auf Haushaltsartikeln nach einem der Ansprüche 1 oder 2, wobei einer oder mehrere Precursor(en) ausgewählt sind aus der Gruppe bestehend aus Fluor und Kohlenstoff enthaltenden Verbindungen und/oder siliciumorganischen Verbindungen. 3. A method for applying easily cleanable surfaces on household articles according to any one of claims 1 or 2, wherein one or more precursor (s) are selected from the group consisting of fluorine and carbon-containing compounds and / or organosilicon compounds.
4. Verfahren zur Aufbringung von leicht reinigbaren Oberflächen auf Haushaltsartikeln nach Anspruch 3, wobei die Fluor und Kohlenstoff enthaltende Verbindung Perfluorocyclobutan (PFCB) ist und die siliciumorganische Verbindung Hexamethyldisiloxan (HMDSO) ist. A method for applying easily cleanable surfaces to household articles according to claim 3, wherein the fluorine and carbon-containing compound is perfluorocyclobutane (PFCB) and the organosilicon compound is hexamethyldisiloxane (HMDSO).
5. Verfahren zur Aufbringung von leicht reinigbaren Oberflächen auf Haushaltsartikeln nach einem der Ansprüche 1 bis 4, wobei die Schichtstärke der abgeschiedenen polymeren Oberflächenschicht etwa 10 nm bis etwa 10 μηη beträgt. A method for applying easily cleanable surfaces to household articles according to any one of claims 1 to 4, wherein the layer thickness of the deposited polymeric surface layer is about 10 nm to about 10 μηη.
6. Verfahren zur Aufbringung von leicht reinigbaren Oberflächen auf Haushaltsartikeln nach einem der Ansprüche 1 bis 5, wobei vor der Abscheidung der polymeren Oberflächenschicht mittels Plasmapolymerisation eine haftvermittelnde Schicht abgeschieden wird. 6. A method for applying easily cleanable surfaces on household articles according to one of claims 1 to 5, wherein before the deposition of the polymeric surface layer by means of plasma polymerization, an adhesion-promoting layer is deposited.
7. Verfahren zur Aufbringung von leicht reinigbaren Oberflächen auf Haushaltsartikeln nach Anspruch 6, wobei die haftvermittelnde Schicht Si02-haltig ist. 7. A method for applying easily cleanable surfaces on household items according to claim 6, wherein the adhesion-promoting layer Si0 2 -containing.
8. Verfahren zur Aufbringung von leicht reinigbaren Oberflächen auf Haushaltsartikeln nach einem der Ansprüche 1 bis 7, wobei vor der Abscheidung der polymeren Oberflächenschicht mittels Plasmapolymerisation der zu beschichtende Teil der Oberfläche angeraut wird. 8. A method for applying easily cleanable surfaces on household articles according to any one of claims 1 to 7, wherein prior to the deposition of the polymeric surface layer by plasma polymerization, the part of the surface to be coated is roughened.
9. Verfahren zur Aufbringung von leicht reinigbaren Oberflächen auf Haushaltsartikeln nach einem der Ansprüche 1 bis 8, wobei mehrere Düsen in einer Reihe angeordnet werden. A method for applying easily cleanable surfaces to household articles according to any one of claims 1 to 8, wherein a plurality of nozzles are arranged in a row.
10. Verfahren zur Aufbringung von leicht reinigbaren Oberflächen auf Haushaltsartikeln nach einem der Ansprüche 1 bis 9, wobei der Haushaltsartikel ein Küchengerät ist. A method of applying easily cleanable surfaces to household articles according to any one of claims 1 to 9, wherein the household article is a kitchen utensil.
1 1. Verfahren zur Aufbringung von leicht reinigbaren Oberflächen auf Haushaltsartikeln nach einem der Ansprüche 1 bis 10, wobei der Haushaltsartikel ein Backofenmuffel ist. 1 1. A method for applying easily cleanable surfaces on household items according to one of claims 1 to 10, wherein the household article is a baking oven muffle.
12. Haushaltsartikel, welcher zumindest eine Teiloberfläche, z.B. bestehend aus Glas, Email, Glaskeramik oder Metall, aufweist, die mit Hilfe des Verfahrens nach einem der Ansprüche 1 bis 1 1 beschichtet wurde, wodurch eine polymere Oberflächenschicht erhalten wird die praktisch keine polaren Gruppen aufweist. 12. Household article which has at least one partial surface, e.g. consisting of glass, enamel, glass-ceramic or metal, which has been coated by the process according to any one of claims 1 to 1 1, whereby a polymeric surface layer is obtained which has virtually no polar groups.
13. Haushaltsartikel nach Anspruch 12, ferner gekennzeichnet dadurch, dass sich zwischen der Teiloberfläche, vorzugsweise bestehend aus Glas, Email, Glaskeramik oder Metall, und der polymeren Oberflächenschicht eine vorzugsweise Si02-haltige haftvermittelnde Schicht befindet. 13. Household article according to claim 12, further characterized in that there is a preferably Si0 2 -containing adhesion-promoting layer between the partial surface, preferably consisting of glass, enamel, glass ceramic or metal, and the polymeric surface layer.
14. Haushaltsartikel nach einem der Ansprüche 12 oder 13, wobei der Haushaltsartikel ein Küchengerät ist. 14. Houseware according to one of claims 12 or 13, wherein the household article is a kitchen appliance.
15. Haushaltsartikel nach einem der Ansprüche 12 bis 14, wobei der Haushaltsartikel ein Backofenmuffel ist. 15. Houseware according to one of claims 12 to 14, wherein the household article is a baking oven muffle.
EP14721389.6A 2013-05-24 2014-05-05 Coating of usage surfaces with plasma polymer layers under atmospheric pressure in order to improve the cleanability Active EP3003581B1 (en)

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DE19833375A1 (en) 1998-07-24 2000-01-27 Weilburger Lackfabrik Jakob Gr An article comprising a coating containing a pigment, fluoropolymer and binder resin, process for its preparation and its use
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