EP1581347B1 - Substrate comprising a polar plasma-polymerised coating - Google Patents

Substrate comprising a polar plasma-polymerised coating Download PDF

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Publication number
EP1581347B1
EP1581347B1 EP20030813057 EP03813057A EP1581347B1 EP 1581347 B1 EP1581347 B1 EP 1581347B1 EP 20030813057 EP20030813057 EP 20030813057 EP 03813057 A EP03813057 A EP 03813057A EP 1581347 B1 EP1581347 B1 EP 1581347B1
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Prior art keywords
nitrogen
coating
oxygen
plasma
polar
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German (de)
French (fr)
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EP1581347A2 (en
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Eva Maria Moser
Heidi Hopp
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Wipf AG
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Wipf AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]

Definitions

  • the invention relates to a method for coating substrates with a polar plasma-polymerized layer of a thickness in the nanometer range, which has long-term stable, multifunctional properties, wherein the process gas contains at least one each substituted hydrocarbon compound and at least one inorganic gas. Furthermore, the invention relates to a coated substrate produced by this process and its use.
  • an organic substrate and a process having a coating consisting of a sub-layer of a plasma-polymerized alkane, for example methane, and a top layer of a plasma-polymerized polar organic component is known.
  • the coating is characterized by improved wettability and hydrophilicity.
  • anhydrous process gases are used, whereby in this use with at least one each Substituted carbon water compound having up to 8 carbon atoms and an organic gas, a previously unattained long-term stability can be achieved.
  • the plasma coating has an initial surface tension of at least 45 mN / m, which remains approximately unchanged for at least one year.
  • the layer thicknesses are generally below 100 nm, that is in the nanometer range.
  • the US 4980196 discloses a method for improving the corrosion resistance of steel by means of a plasma coating.
  • a steel substrate is coated with a thin organosilane film. This document does not address the issue of coating other substrates, nor does it disclose the preparation of a two-layer coating.
  • Polar plasma layers containing oxygen- and / or nitrogen-containing functional groups can be prepared already at much higher pressures than in low-pressure processes, u. a. because a certain amount of air does not harm the processes, but can even be useful, a pressure range of up to 1000 mbar is possible. Under these conditions, virtually all known plasma coating techniques, for planar or three-dimensional workpieces, can be used.
  • the plasma layer according to the invention can be connected upstream or downstream of virtually any production step, irrespective of whether the workpiece has already been introduced into a vacuum chamber and subsequently z. B. metallization takes place or whether it is an occurring at atmospheric adhesion promoter coating before printing. Furthermore, the workpiece can be used directly as an anti-fog functional layer.
  • the surface of the plasma-coated workpieces may be smoother than that untreated substrate. Smoother surface contours favor surface wetting and thus the essential antifogging effect.
  • the nitrogen-containing process gases of the first zone or stage ensure good anchoring of the plasma layer on the substrate and, on the other hand, depending on the control of the process parameters (power, gas mixture), more or less pronounced smoothing and / or structuring or modulating the surface. For this effect, the corrosive action of aggressive gases, such as nitrous oxide, ammonia and oxygen, is decisive in the first place, especially when these gases are metered in with an increased proportion.
  • XPS X-ray photoelectron spectroscopy
  • the plasma-polymerized layers deposited according to the invention are distinguished by their controllable multifunctionality; by varying parameters, the plasma layer can be adapted to the respective application. All plasma-polymerized layers produced according to the invention have long-term stability in common. Another, usually required property is a permanent high surface tension of the plasma-polymerized polar layers, which are therefore hydrophilic, which also means a good adhesion to emulsion paints. Further examples of the multifunctionality of the polar layers are the mentioned antifogging effect, the formation of a scratch-resistant layer, a barrier layer against additives, gases and liquids, which on the one hand migrate from the substrate to the surface or can be deposited on the surface of the environment, or a flame retardant layer.
  • the plasma-polymerized layers are preferably deposited at a process pressure p between 10 -3 and 1000 mbar, in particular between 0.1 and 500 mbar.
  • the process pressure is significant for the reasons mentioned higher than in comparable conventional methods, in particular as according to the WO 99/39842 , Expediently, the plasma reactor is previously pumped down to a base pressure which is lower than the process pressure, preferably at least approximately ten times lower, and then filled with process gas. After a coating process below 1000 mbar, the plasma reactor is flooded with, for example, air, nitrogen or argon until the normal pressure is reached and the reactor can be opened. Flooding with argon is too expensive for most processes, air is usually sufficient for this.
  • the organic compound in the process gas may be a pure hydrocarbon compound or a hydrocarbon compound having substituted functional groups, especially oxygen- and / or nitrogen-containing polar functional groups.
  • acetylene C 2 H 2 , ethyne
  • the other process gases contribute to the functional groups and can thereby also remove atomic layers from the surface.
  • the hydrocarbons may, as mentioned, be substituted with halogens, such as chlorine and / or fluorine, or with functional polar groups.
  • halogens such as chlorine and / or fluorine
  • functional polar groups are hydroxyl, carbonyl, carboxylic acid, carboxyl ester, amine, imine, amide and / or conjugated nitrile groups.
  • SiO x -containing functional groups are additionally generated in the lower and / or upper layer, thereby increasing the oxygen content. It is also possible in some cases for C atoms to be replaced by Si atoms.
  • the molecules For both substituted and unsubstituted hydrocarbon compounds, it is advantageous if the molecules contain up to a maximum of eight carbon atoms.
  • the inorganic component of the process gases advantageously comprises oxygen, carbon dioxide, carbon monoxide, nitrogen, NOx, ammonia, hydrogen, at least one halogen and / or at least one noble gas, but is preferably anhydrous.
  • the process gases for the deposition of the lower and upper layers differ fundamentally only in terms of nitrogen and / or oxygen content.
  • the inventive two-stage coating is particularly indicated for food packaging. It has been found that nitrogen-containing gases purify the substrate surface to form a CN bond. This also leads to a better anchoring of the functional polar groups, which in turn has a higher chemical resistance. On this lower layer, which can also be very thin, z. B. about 0.3 nm, a nitrogen-free, oxygen-containing upper layer is still deposited, so that the nitrogen-containing layer can not come into contact with food or other nitrogen-sensitive objects.
  • two plasma sources are used.
  • a nitrogen-oxygen-hydrocarbon-containing gas mixture is supplied and a lower layer is deposited on the substrate.
  • the second zone / plasma source is made of a nitrogen-free, oxygen-hydrocarbon Process gas mixture deposited an upper layer on the lower layer.
  • Plasma chambers with two plasma sources, as used herein, are known in the art.
  • a single plasma source can be used and first the nitrogen-hydrocarbon-containing or nitrogen-oxygen-hydrocarbon-containing gas mixture, the oxygen-hydrocarbon-containing process gas mixture can be introduced during the second pass.
  • the object is achieved according to the invention in that a nanometer-scale plasma-polymerized polar layer is applied as a nitrogen-containing underlayer applied to the substrate and a nitrogen-free, oxygen-containing polar upper layer applied thereto.
  • a nanometer-scale plasma-polymerized polar layer is applied as a nitrogen-containing underlayer applied to the substrate and a nitrogen-free, oxygen-containing polar upper layer applied thereto.
  • the nitrogen-containing underlayer preferably has a proportion of 40 to 90% of the total layer thickness, the polar upper layer a proportion of 60 to 10% of the total layer thickness, preferably about 50% each.
  • the total layer thickness is preferably in the range from 1 to 100 nm.
  • the oxygen / carbon ratio is preferably in the range of 0.03 to 0.8, in the lower layer, the ratio of nitrogen / carbon in the same range.
  • the polar upper layer averaged in the uppermost about 2 nm, ie at the surface, preferably has an oxygen / carbon ratio of from 0.2 to 0.6, preferably from 0.3 to 0.5 and a durable surface tension of at least 50 mN / m.
  • the oxygen content-increasing carboxyl groups can be formed on the surface of the upper layer. With the high surface tension in particular a good antifogging effect is ensured especially with a suitable surface topography.
  • the inventive layer can be deposited on all types of substrates, for example on polymeric, glassy, ceramic, metallic or natural surfaces, in particular a polycarbonate, polyethylene terephthalate, polypropylene, polyethylene, polyamide, fluoropolymers, wool, cotton, silk, glass, ceramic or also composite materials or composite materials, all materials (including natural) in the form of films, moldings, containers, textiles, nonwovens, membranes, granules, powders, fibers, lattices and yarns, containers as well as in the form of coated or activated or treated surfaces of materials all kinds.
  • substrates for example on polymeric, glassy, ceramic, metallic or natural surfaces, in particular a polycarbonate, polyethylene terephthalate, polypropylene, polyethylene, polyamide, fluoropolymers, wool, cotton, silk, glass, ceramic or also composite materials or composite materials, all materials (including natural) in the form of films, moldings, containers, textiles, nonwovens, membranes, granules, powder
  • a product according to the invention is determined by means of an in Fig. 1 illustrated schematically layer structure.
  • This figure shows a coated substrate 10 having a substrate 12, a backsheet 14, and a topsheet 16.
  • the two polar plasma polymerized layers 14, 16 herein have a total thickness, d, of about 10 nm herein.
  • the backsheet 14 is nitrogenous, has excellent properties Adhesion to the substrate 12 on.
  • a disadvantage could be a possible amine formation because of the lower layer 14 impact. This disadvantage is prevented by the oxygen-containing, but low-nitrogen to nitrogen-free upper layer 16.
  • a thin underlayer 14 is deposited on a substrate 12 with a 2.45 GHz microwave source using a process gas mixture of ethylene, carbon dioxide, nitrous oxide and argon introduced in the first zone at the plasma source or at the first plasma source.
  • the gas mixture of acetylene, carbon dioxide and argon is introduced to produce the top layer.
  • polyester, polypropylene were used on the substrates and polyethylene surface tensions of 54 to 75 mN / m, which have a polar fraction of 23 to 51 mN / m and are characterized with an oxygen to carbon ratio of 0.3 to 0.5 and a carboxyl to carbonyl groups ratio of 0.2 to 1.2.
  • the surface tension can be controlled by the feed rate.
  • the oxygen to carbon ratio and the ratio of carboxyl to carbonyl groups in the top atomic layers of the deposited layers were determined by surface-sensitive XPS (photoelectron spectroscopy).
  • the same layer properties can also be achieved with all other types of discharge, each with excitation frequencies from zero to 20 GHz and in each case with or without magnetic field support.
  • Exemplary are DBDs (Dielectric Barrier Discharges), low pressure to atmospheric pressure glow discharges, atmospheric pressure non-equilibrium Discharges (APNEDs), surface dicarges, plasma jets and plasma jet burners.
  • DBDs Dielectric Barrier Discharges
  • ANEDs atmospheric pressure non-equilibrium Discharges
  • surface dicarges plasma jets and plasma jet burners.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Laminated Bodies (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Chemical Vapour Deposition (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

Substrates which are coated with a polar plasma-polymerized coating of a thickness (d) in the nanometer range, the coating having multi-functional properties with long-term stability. The process gas contains at least one hydrocarbon that can be substituted and at least one inorganic gas. In a first zone or stage, the substrate is coated using process gases that contain at least one hydrocarbon compound, at least one hydrocarbon compound comprising functional groups containing nitrogen or nitrogen and oxygen and/or at least one inorganic gas containing nitrogen or nitrogen and oxygen. A second zone or stage uses process gases that are devoid of nitrogen and comprise at least one hydrocarbon compound, at least one hydrocarbon compound with functional groups that contain oxygen and/or at least one inorganic gas containing oxygen. The two stages permit a corresponding lower and upper coating to be applied to the substrate.

Description

Die Erfindung bezieht sich auf ein Verfahren zum Beschichten von Substraten mit einer polaren plasmapolymerisierten Schicht einer Dicke im Nanometerbereich, welche langzeitstabile, multifunktionale Eigenschaften aufweist, wobei das Prozessgas wenigstens je eine auch substituierte Kohlenwasserstoffverbindung und wenigstens ein anorganisches Gas enthält. Weiter betrifft die Erfindung ein nach diesem Verfahren hergestelltes beschichtetes Substrat und dessen Verwendung.The invention relates to a method for coating substrates with a polar plasma-polymerized layer of a thickness in the nanometer range, which has long-term stable, multifunctional properties, wherein the process gas contains at least one each substituted hydrocarbon compound and at least one inorganic gas. Furthermore, the invention relates to a coated substrate produced by this process and its use.

Es ist seit einiger Zeit bekannt, Substrate aller Art mit einer dünnen plasmapolymerisierten Schicht zu überziehen. Die ursprünglich schlechte Haftung von Farben, Lack usw. auf dem Substrat und/oder die schlechte Benetzbarkeit des Substrats konnte mit der Einführung von Niederdruckplasma-Verfahren verbessert werden, insbesondere auch bezüglich der Langzeitwerte. Die Beschichtung von Substraten, insbesondere auch von flexiblen polymeren Substraten, erfolgt unter anderem mit Blick auf die Oberflächenbeschaffenheit. Oft ist es auch erforderlich, das Substrat chemisch, physikalisch und/oder mechanisch zu schützen. Wenn die plasmapolymerisierte Schicht mehrere Funktionen gleichzeitig zu übernehmen hat, wird von einer multifunktionalen Schicht gesprochen.It has been known for some time to coat substrates of all kinds with a thin plasma polymerized layer. The originally poor adhesion of paints, varnishes etc. to the substrate and / or the poor wettability of the substrate could be improved with the introduction of low-pressure plasma processes, in particular also with respect to the long-term values. The coating of substrates, in particular also of flexible polymeric substrates, takes place inter alia with a view to the surface condition. Often it is also necessary to protect the substrate chemically, physically and / or mechanically. If the plasma-polymerized layer has to perform several functions at the same time, it is referred to as a multifunctional layer.

Aus der US 4465738 A ist ein organisches Substrat und ein Verfahren mit einer Beschichtung bekannt, die aus einer Unterschicht aus einem plasmapolymerisierten Alkan, beispielsweise Methan, und einer Oberschicht aus einer plasmapolymerisierten polaren organischen Komponente besteht. Die Beschichtung zeichnet sich durch eine verbesserte Benetzbarkeit und Hydrophilie aus.From the US 4465738 A For example, an organic substrate and a process having a coating consisting of a sub-layer of a plasma-polymerized alkane, for example methane, and a top layer of a plasma-polymerized polar organic component is known. The coating is characterized by improved wettability and hydrophilicity.

Ein Durchbruch ist mit der WO 99/39842 A1 gelungen. Zur Herstellung einer polaren Beschichtung mittels Plasmapolymerisation werden wasserfreie Prozessgase eingesetzt, wodurch bei diesem Einsatz mit mindestens je einer auch substituierten Kohlenstoffwasserverbindung mit bis zu 8 C-Atomen und einem organischen Gas eine bisher nicht erreichte Langzeitstabilität erreicht werden kann. Die Plasmabeschichtung weist eine initiale Oberflächenspannung von wenigstens 45 mN/m auf, welche während mindestens einem Jahr etwa unverändert bleibt. Die Schichtdicken liegen in der Regel unter 100 nm, sind also im Nanometerbereich. Zur Durchführung des Verfahrens sind gemäss dem die Seiten 5 und 6 der WO 99/39842 A1 überbrückenden Absatz alle Niederdruckplasma-Verfahren geeignet beispielsweise bei einem Druck von 1.6 x 10-2 mbar. Eine Serie von Beispielen ist in Tabelle 1 der WO 99/39842 A1 zusammengefasst. Die Verwendung dieser polaren, langzeitstabilen Schichten ist infolge der Haftvermittlung, d. h. der verbesserten Adhäsion gegenüber polaren Substanzen und Materialien, ausserordentlich vielfältig, besonders zu erwähnen ist die Bedruckbarkeit, der Kratzschutz, eine Antifog-Wirkung und die Verschweissbarkeit.A breakthrough is with the WO 99/39842 A1 succeeded. To produce a polar coating by means of plasma polymerization anhydrous process gases are used, whereby in this use with at least one each Substituted carbon water compound having up to 8 carbon atoms and an organic gas, a previously unattained long-term stability can be achieved. The plasma coating has an initial surface tension of at least 45 mN / m, which remains approximately unchanged for at least one year. The layer thicknesses are generally below 100 nm, that is in the nanometer range. To carry out the method according to the pages 5 and 6 of WO 99/39842 A1 bridging paragraph all low pressure plasma method suitable for example at a pressure of 1.6 x 10 -2 mbar. A series of examples is shown in Table 1 WO 99/39842 A1 summarized. The use of these polar, long-term stable layers is due to the adhesion, ie the improved adhesion to polar substances and materials, extremely diverse, especially worth mentioning is the printability, the scratch protection, an anti-fog effect and the weldability.

Die US 4980196 offenbart ein Verfahren zur Verbesserung der Korrosionsfestigkeit von Stahl mit Hilfe einer Plasmabeschichtung. Hierbei wird ein Stahlsubstrat mit einem dünnen Organosilanfilm beschichtet. Dieses Dokument geht nicht auf die Frage der Beschichtung anderer Substrate ein, und offenbart ferner nicht die Herstellung einer zweischichtigen Beschichtung.The US 4980196 discloses a method for improving the corrosion resistance of steel by means of a plasma coating. Here, a steel substrate is coated with a thin organosilane film. This document does not address the issue of coating other substrates, nor does it disclose the preparation of a two-layer coating.

Der vorliegenden Patentanmeldung liegt die Aufgabe zugrunde, ein Verfahren zum Beschichten von Substraten verschiedenster Art mit einer plasmapolymerisierten Schicht und ein Erzeugnis der eingangs genannten Art zu schaffen, welche auch bei erweiterter Substratbasis die Eigenschaften nochmals verbessern, insbesondere die Adhäsion auf der plasmapolymerisierten Schicht und dieser Schicht auf dem Substrat erhöhen.It is an object of the present patent application to provide a process for coating various types of substrates with a plasma-polymerized layer and a product of the type mentioned above which, even with an extended substrate base, further improve the properties, in particular the adhesion to the plasma-polymerized layer and this layer increase on the substrate.

In bezug auf das Verfahren wird die Aufgabe erfindungsgemäss dadurch gelöst, dass

  • in einer ersten Zone oder Stufe mit Prozessgasen, die wenigstens eine Kohlenwasserstoffverbindung, wenigstens eine Kohlenwasserstoffverbindung mit stickstoffhaltigen oder stickstoff- und sauerstoffhaltigen funktionellen Gruppen und/oder wenigstens ein stickstoffhaltiges oder ein stickstoff- und sauerstoffhaltiges anorganisches Gas enthalten,
  • in einer zweiten Zone oder Stufe mit stickstofffreien Prozessgasen, die wenigstens eine Kohlenwasserstoffverbindung, wenigstens eine Kohlenwas-serstoffverbindung mit sauerstoffhaltigen funktionellen Gruppen und/oder wenigstens ein sauerstoffhaltiges anorganisches Gas enthalten,
beschichtet wird. Spezielle und weiterbildende Ausführungsformen des Verfahrens sind Gegenstand von abhängigen Patentansprüchen.With regard to the method, the object is achieved according to the invention in that
  • in a first zone or stage with process gases containing at least one hydrocarbon compound, at least one hydrocarbon compound having nitrogen-containing or nitrogen- and oxygen-containing functional groups and / or at least one nitrogen-containing or nitrogen-containing and oxygen-containing inorganic gas,
  • in a second zone or stage with nitrogen-free process gases containing at least one hydrocarbon compound, at least one hydrocarbon compound containing oxygen-containing functional groups and / or at least one oxygen-containing inorganic gas,
is coated. Specific and further developing embodiments of the method are the subject of dependent claims.

Mit dem erfindungsgemässen Verfahren sind unter Verwendung von effizienten Gasgemischen, welche unabhängig vom Druckbereich und von der Entladungsart anwendbar sind, langzeitstabile, plasmapolymerisierte polare Schutzschichten möglich. Es wird ein Weg für die Kombination von mehreren Schichten für multifunktionale Eigenschaften aufgezeigt. Bei mehr als zwei Schichten ist erfindungswesentlich, dass die direkt auf dem Substrat abgeschiedene Schicht stickstoffhaltig, die oberste Schicht stickstofffrei, aber sauerstoffhaltig ist.With the method according to the invention, long-term stable, plasma-polymerized polar protective layers are possible using efficient gas mixtures which are applicable independently of the pressure range and the type of discharge. A way is shown for the combination of multiple layers for multifunctional properties. In the case of more than two layers, it is essential to the invention that the layer deposited directly on the substrate contains nitrogen, and the uppermost layer is nitrogen-free, but oxygen-containing.

Polare Plasmaschichten, welche sauerstoff- und/oder stickstoffhaltige funktionelle Gruppen enthalten, können schon bei weit höheren Drucken als in Niederdruckverfahren üblich hergestellt werden, u. a. weil ein gewisser Anteil von Luft den Prozessen nicht schadet, sondern sogar dienlich sein kann, ist ein Druckbereich bis 1000 mbar möglich. Unter diesen Voraussetzungen können praktisch alle bekannten Plasmabeschichtungstechniken, für planare oder dreidimensionale Werkstücke, eingesetzt werden.Polar plasma layers containing oxygen- and / or nitrogen-containing functional groups can be prepared already at much higher pressures than in low-pressure processes, u. a. because a certain amount of air does not harm the processes, but can even be useful, a pressure range of up to 1000 mbar is possible. Under these conditions, virtually all known plasma coating techniques, for planar or three-dimensional workpieces, can be used.

Die erfindungsgemässe Plasmaschicht kann nahezu beliebig einem Produktionsschritt vorgeschaltet oder nachgeschaltet werden, gleichgültig ob das Werkstück bereits in einer Vakuumkammer eingeschleust wurde und anschliessend z. B. eine Metallisierung stattfindet oder ob es sich um eine bei Atmosphärendruck stattfindende haftvermittelnde Beschichtung vor einer Bedruckung handelt. Weiter kann das Werkstück direkt als Antifog-Funktionsschicht verwendet werden.The plasma layer according to the invention can be connected upstream or downstream of virtually any production step, irrespective of whether the workpiece has already been introduced into a vacuum chamber and subsequently z. B. metallization takes place or whether it is an occurring at atmospheric adhesion promoter coating before printing. Furthermore, the workpiece can be used directly as an anti-fog functional layer.

Die Oberfläche der plasmabeschichteten Werkstücke kann glatter sein als das unbehandelte Substrat. Sanftere Oberflächenkonturen begünstigen die Oberflächenbenetzung und damit den hier wesentlichen Antifog-Effekt. Die stickstoffhaltigen Prozessgase der ersten Zone oder Stufe bewirken einerseits eine gute Verankerung der Plasmaschicht auf dem Substrat und können andererseits je nach Steuerung der Prozessparameter (Leistung, Gasgemisch) die Oberfläche mehr oder weniger ausgeprägt glätten und/oder strukturieren, bzw. zu modulieren. Für diesen Effekt ist in erster Linie die ätzende Wirkung von aggressiven Gasen, wie z.B. Lachgas, Ammoniak und Sauerstoff massgebend, insbesondere wenn diese Gase mit erhöhtem Anteil zudosiert werden.The surface of the plasma-coated workpieces may be smoother than that untreated substrate. Smoother surface contours favor surface wetting and thus the essential antifogging effect. The nitrogen-containing process gases of the first zone or stage, on the one hand, ensure good anchoring of the plasma layer on the substrate and, on the other hand, depending on the control of the process parameters (power, gas mixture), more or less pronounced smoothing and / or structuring or modulating the surface. For this effect, the corrosive action of aggressive gases, such as nitrous oxide, ammonia and oxygen, is decisive in the first place, especially when these gases are metered in with an increased proportion.

XPS (Röntgen-Photoelektronen-Spektroskopie)-Messungen belegen, bzw. bestätigen die erwartete Anreicherung mit Sauerstoff und Stickstoff und die Einbindung von Sauerstoff, insbesondere als Hydroxyl-, Carbonyl- oder Carboxyl (Ester) - Gruppen.XPS (X-ray photoelectron spectroscopy) measurements confirm or confirm the expected enrichment with oxygen and nitrogen and the incorporation of oxygen, especially as hydroxyl, carbonyl or carboxyl (ester) groups.

Die erfindungsgemäss abgeschiedenen plasmapolymerisierten Schichten zeichnen sich durch ihre steuerbare Multifunktionalität aus, durch Variation von Parametern kann die Plasmaschicht der jeweiligen Anwendung angepasst werden. Allen erfindungsgemäss hergestellten plasmapolymerisierten Schichten ist die Langzeitstabilität gemeinsam. Eine weitere, meist erforderliche Eigenschaft ist eine dauerhafte hohe Oberflächenspannung der plasmapolymerisierten polaren Schichten, welche dadurch hydrophil sind, was auch eine gute Haftvermittlung gegenüber Dispersionsfarben bedeutet. Weitere Beispiele für die Multifunktionalität der polaren Schichten sind die erwähnte Antifog-Wirkung, die Ausbildung einer Kratzschutzschicht, einer Barriereschicht gegenüber Additiven, Gasen und Flüssigkeiten, welche einerseits aus dem Substrat an die Oberfläche migrieren oder von der Umgebung an der Oberfläche abgelagert werden können, oder einer Flammschutzschicht.The plasma-polymerized layers deposited according to the invention are distinguished by their controllable multifunctionality; by varying parameters, the plasma layer can be adapted to the respective application. All plasma-polymerized layers produced according to the invention have long-term stability in common. Another, usually required property is a permanent high surface tension of the plasma-polymerized polar layers, which are therefore hydrophilic, which also means a good adhesion to emulsion paints. Further examples of the multifunctionality of the polar layers are the mentioned antifogging effect, the formation of a scratch-resistant layer, a barrier layer against additives, gases and liquids, which on the one hand migrate from the substrate to the surface or can be deposited on the surface of the environment, or a flame retardant layer.

Die plasmapolymerisierten Schichten werden bevorzugt bei einem Prozessdruck p zwischen 10-3 und 1000 mbar, insbesondere zwischen 0,1 und 500 mbar, abgeschieden. Der Prozessdruck liegt aus den erwähnten Gründen bedeutend höher als bei vergleichbaren üblichen Verfahren, insbesondere auch als nach der WO 99/39842 . Zweckmässig wird der Plasmareaktor vorgängig bis zu einem Basisdruck, der tiefer ist als der Prozessdruck liegt, vorzugsweise wenigstens etwa zehnmal tiefer, abgepumpt, anschliessend mit Prozessgas gefüllt. Nach einem Beschichtungsprozess unterhalb 1000 mbar wird der Plasmareaktor mit beispielsweise Luft, Stickstoff oder Argon geflutet, bis der Normaldruck erreicht ist und der Reaktor geöffnet werden kann. Das Fluten mit Argon ist für die meisten Prozesse zu teuer, Luft ist dafür meistens ausreichend.The plasma-polymerized layers are preferably deposited at a process pressure p between 10 -3 and 1000 mbar, in particular between 0.1 and 500 mbar. The process pressure is significant for the reasons mentioned higher than in comparable conventional methods, in particular as according to the WO 99/39842 , Expediently, the plasma reactor is previously pumped down to a base pressure which is lower than the process pressure, preferably at least approximately ten times lower, and then filled with process gas. After a coating process below 1000 mbar, the plasma reactor is flooded with, for example, air, nitrogen or argon until the normal pressure is reached and the reactor can be opened. Flooding with argon is too expensive for most processes, air is usually sufficient for this.

Die organische Verbindung im Prozessgas kann eine reine Kohlenwasserstoffverbindung oder eine Kohlenwasserstoffverbindung mit substituierten funktionellen Gruppen sein, insbesondere sauerstoff- und/oder stickstoffhaltige polare funktionelle Gruppen.The organic compound in the process gas may be a pure hydrocarbon compound or a hydrocarbon compound having substituted functional groups, especially oxygen- and / or nitrogen-containing polar functional groups.

Die Kohlenwasserstoffverbindungen selbst können verschiedenster Natur sein:

  • Alkane, beispielsweise Methan, Ethan, Propan
  • Alkene, beispielsweise Ethylen, Propylen
  • Alkine, beispielsweise Acethylen
  • Polyene, d.h. Kohlenwasserstoffe mit mehreren Doppelbindungen
jeweils in aliphatischer, alicyclischer oder aromatischer Ausbildung, ohne oder mit Verzweigung/en.The hydrocarbon compounds themselves can be of various types:
  • Alkanes, for example methane, ethane, propane
  • Alkenes, for example ethylene, propylene
  • Alkynes, for example, acetylene
  • Polyenes, ie hydrocarbons with multiple double bonds
each in aliphatic, alicyclic or aromatic form, with or without branching.

Als schichtbildendes Prozessgas wird insbesondere Acethylen (C2H2, Ethin) verwendet, die anderen Prozessgase steuern die funktionalen Gruppen bei und können dadurch auch atomare Lagen von der Oberfläche abtragen.In particular, acetylene (C 2 H 2 , ethyne) is used as the layer-forming process gas; the other process gases contribute to the functional groups and can thereby also remove atomic layers from the surface.

Die Kohlenwasserstoffe können, wie erwähnt, mit Halogenen, wie Chlor und/oder Fluor, oder mit funktionellen polaren Gruppen substituiert sein. Beispiele von funktionellen polaren Gruppen sind Hydroxyl-, Carbonyl-, Carboxylsäure-, Carboxylester-, Amin-, Imin-, Amid- und/oder conjugierte Nitrilgruppen.The hydrocarbons may, as mentioned, be substituted with halogens, such as chlorine and / or fluorine, or with functional polar groups. Examples of functional polar groups are hydroxyl, carbonyl, carboxylic acid, carboxyl ester, amine, imine, amide and / or conjugated nitrile groups.

Bei einer Zumischung von siliziumhaltigen Prozessgasen werden in der Unter- und/oder Oberschicht zusätzlich SiOx-haltige funktionelle Gruppen erzeugt und dadurch der Sauerstoffgehalt erhöht. Dabei können auch teilweise C-Atome durch Si-Atome ersetzt werden.When mixing silicon-containing process gases, SiO x -containing functional groups are additionally generated in the lower and / or upper layer, thereby increasing the oxygen content. It is also possible in some cases for C atoms to be replaced by Si atoms.

Sowohl für substituierte als auch für nicht substituierte Kohlenwasserstoffverbindungen ist es vorteilhaft, wenn die Moleküle bis maximal acht C-Atome enthalten.For both substituted and unsubstituted hydrocarbon compounds, it is advantageous if the molecules contain up to a maximum of eight carbon atoms.

Die anorganische Komponente der Prozessgase umfasst vorteilhaft Sauerstoff, Kohlenstoffdioxid, Kohlenstoffmonoxid, Stickstoff, NOx, Ammoniak, Wasserstoff, wenigstens ein Halogen und/oder wenigstens ein Edelgas, ist jedoch vorzugsweise wasserfrei.The inorganic component of the process gases advantageously comprises oxygen, carbon dioxide, carbon monoxide, nitrogen, NOx, ammonia, hydrogen, at least one halogen and / or at least one noble gas, but is preferably anhydrous.

Die Prozessgase für die Abscheidung der Unter- und Oberschicht unterscheiden sich grundsätzlich nur bezüglich des Stickstoff- und/oder Sauerstoffgehalts.The process gases for the deposition of the lower and upper layers differ fundamentally only in terms of nitrogen and / or oxygen content.

Die erfindungsgemässe zweistufige Beschichtung ist insbesondere auch für Lebensmittelverpackungen angezeigt. Es hat sich herausgestellt, dass stickstoffhaltige Gase unter Bildung einer CN-Bindung die Substratoberfläche reinigen. Dies führt zudem zu einer besseren Verankerung der funktionellen polaren Gruppen, was wiederum eine höhere chemische Beständigkeit zur Folge hat. Auf dieser Unterschicht, welche auch sehr dünn sein kann, z. B. etwa 0,3 nm, wird noch eine stickstofffreie, sauerstoffhaltige Oberschicht abgeschieden, damit die stickstoffhaltige Schicht nicht in Kontakt mit Lebensmitteln oder anderen stickstoffempfindlichen Objekten kommen kann.The inventive two-stage coating is particularly indicated for food packaging. It has been found that nitrogen-containing gases purify the substrate surface to form a CN bond. This also leads to a better anchoring of the functional polar groups, which in turn has a higher chemical resistance. On this lower layer, which can also be very thin, z. B. about 0.3 nm, a nitrogen-free, oxygen-containing upper layer is still deposited, so that the nitrogen-containing layer can not come into contact with food or other nitrogen-sensitive objects.

Für das Abscheiden einer Unter- und einer Oberschicht werden vorteilhaft zwei Plasmaquellen eingesetzt. Bei der ersten Zone/Plasmaquelle wird beispielsweise ein stickstoff-sauerstoff-kohlenwasserstoffhaltiges Gasgemisch zugeführt und eine Unterschicht auf das Substrat abgeschieden. Mit der zweiten Zone/Plasmaquelle wird aus einem stickstofffreien, sauerstoff-kohlenwasserstoffhaltigen Prozessgasgemisch eine Oberschicht auf die Unterschicht abgeschieden. Plasmakammern mit zwei Plasmaquellen, wie sie hier verwendet werden, sind dem Fachmann bekannt.For the deposition of a lower and an upper layer advantageously two plasma sources are used. In the first zone / plasma source, for example, a nitrogen-oxygen-hydrocarbon-containing gas mixture is supplied and a lower layer is deposited on the substrate. With the second zone / plasma source is made of a nitrogen-free, oxygen-hydrocarbon Process gas mixture deposited an upper layer on the lower layer. Plasma chambers with two plasma sources, as used herein, are known in the art.

Nach einer weiteren Variante kann eine einzige Plasmaquelle eingesetzt und zuerst das stickstoff-kohlenwasserstoffhaltige oder stickstoff-sauerstoff-kohlenwasserstoffhaltige Gasgemisch, beim zweiten Durchlauf das sauerstoff-kohlenwasserstoffhaltige Prozessgasgemisch eingeleitet werden.According to a further variant, a single plasma source can be used and first the nitrogen-hydrocarbon-containing or nitrogen-oxygen-hydrocarbon-containing gas mixture, the oxygen-hydrocarbon-containing process gas mixture can be introduced during the second pass.

In Bezug auf das Erzeugnis wird die Aufgabe erfindungsgemäss dadurch gelöst, dass eine plasmapolymerisierte polare Schicht im Nanometerbereich als eine auf das Substrat aufgebrachte stickstoffhaltige Unterschicht und eine darauf aufgebrachte stickstofffreie, sauerstoffhaltige polare Oberschicht aufgetragen ist. Spezielle und weiterbildende Ausführungsformen des Erzeugnisses ergeben sich aus den abhängigen Patentansprüchen.With regard to the product, the object is achieved according to the invention in that a nanometer-scale plasma-polymerized polar layer is applied as a nitrogen-containing underlayer applied to the substrate and a nitrogen-free, oxygen-containing polar upper layer applied thereto. Special and further developing embodiments of the product result from the dependent claims.

Die stickstoffhaltige Unterschicht hat vorzugsweise einen Anteil von 40 bis 90% der gesamten Schichtdicke, die polare Oberschicht einen Anteil von 60 bis 10% der gesamten Schichtdicke, vorzugsweise je etwa 50%. Die gesamte Schichtdicke liegt bevorzugt im Bereich von 1 bis 100 nm. Die beschichteten Substrate sind miteinander verschweissbar.The nitrogen-containing underlayer preferably has a proportion of 40 to 90% of the total layer thickness, the polar upper layer a proportion of 60 to 10% of the total layer thickness, preferably about 50% each. The total layer thickness is preferably in the range from 1 to 100 nm. The coated substrates can be welded together.

In einer Schicht, mit einer Unter- und Oberschicht aus Kohlenwasserstoffverbindungen mit sauerstoffhaltigen funktionellen Gruppen liegt das Sauerstoff/Kohlenstoff-Verhältnis vorzugsweise im Bereich von je 0,03 bis 0,8, in der Unterschicht liegt das Verhältnis Stickstoff / Kohlenstoff im gleichen Bereich.
Die polare Oberschicht hat, gemittelt in den obersten etwa 2 nm, d.h. an der Oberfläche, bevorzugt ein Sauerstoff / Kohlenstoff - Verhältnis von 0,2 bis 0,6, vorzugsweise von 0,3 bis 0,5 und eine dauerhafte Oberflächenspannung von wenigstens 50 mN/m. An der Oberfläche der Oberschicht können den Sauerstoffgehalt heraufsetzende Carboxylgruppen gebildet werden. Mit der hohen Oberflächenspannung ist insbesondere eine gute Antifog-Wirkung gewährleistet, insbesondere mit einer geeigneten Oberflächentopographie.In a layer with a lower and upper layer of hydrocarbon compounds having oxygen-containing functional groups, the oxygen / carbon ratio is preferably in the range of 0.03 to 0.8, in the lower layer, the ratio of nitrogen / carbon in the same range.
The polar upper layer, averaged in the uppermost about 2 nm, ie at the surface, preferably has an oxygen / carbon ratio of from 0.2 to 0.6, preferably from 0.3 to 0.5 and a durable surface tension of at least 50 mN / m. On the surface of the upper layer, the oxygen content-increasing carboxyl groups can be formed. With the high surface tension in particular a good antifogging effect is ensured especially with a suitable surface topography.

Die erfindungsgemässe Schicht lässt sich auf alle Arten von Substraten abscheiden, beispielsweise auf polymere, glasartige, keramische, metallische oder natürliche Oberflächen, insbesondere auf ein Polycarbonat, Polyethylenterephthalat, Polypropylen, Polyethylen, Polyamid, Fluoropolymere, Wolle, Baumwolle, Seide, Glas, Keramik oder auch Kompositwerkstoffe oder Verbundwerkstoffe, alle Materialien (auch natürliche) in Form von Folien, Formkörpern, Behältern, Textilien, Vliesstoffen, Membranen, Granulatkörnern, Pulver, Fasern, Gittern und Garnen, Behältern sowie auch in Form beschichteten oder aktivierten bzw. behandelten Oberflächen von Materialien aller Art.The inventive layer can be deposited on all types of substrates, for example on polymeric, glassy, ceramic, metallic or natural surfaces, in particular a polycarbonate, polyethylene terephthalate, polypropylene, polyethylene, polyamide, fluoropolymers, wool, cotton, silk, glass, ceramic or also composite materials or composite materials, all materials (including natural) in the form of films, moldings, containers, textiles, nonwovens, membranes, granules, powders, fibers, lattices and yarns, containers as well as in the form of coated or activated or treated surfaces of materials all kinds.

Ein erfindungsgemässes Erzeugnis wird anhand eines in Fig. 1 schematisch dargestellten Schichtaufbaus näher erläutert. Diese Figur zeigt ein beschichtetes Substrat 10 mit einem Substrat 12, einer Unterschicht 14 und einer Oberschicht 16. Die beiden polaren plasmapolymerisierten Schichten 14, 16 haben vorliegend eine gesamte Dicke d von vorliegend etwa 10 nm. Die Unterschicht 14 ist stickstoffhaltig, sie weist eine ausgezeichnete Adhäsion zum Substrat 12 auf. Nachteilig könnte sich eine mögliche Aminbildung wegen der Unterschicht 14 auswirken. Dieser Nachteil wird durch die sauerstoffhaltige, jedoch stickstoffarme bis stickstofffreie Oberschicht 16 verhindert.A product according to the invention is determined by means of an in Fig. 1 illustrated schematically layer structure. This figure shows a coated substrate 10 having a substrate 12, a backsheet 14, and a topsheet 16. The two polar plasma polymerized layers 14, 16 herein have a total thickness, d, of about 10 nm herein. The backsheet 14 is nitrogenous, has excellent properties Adhesion to the substrate 12 on. A disadvantage could be a possible amine formation because of the lower layer 14 impact. This disadvantage is prevented by the oxygen-containing, but low-nitrogen to nitrogen-free upper layer 16.

Beispiel: Multischichtabscheidung mit einer MiktrowellenentladungExample: Multi-layer separation with a microwave discharge

Es wird eine dünne Unterschicht 14 auf ein Substrat 12 mit einer Mikrowellenquelle bei 2.45 GHz abgeschieden, unter Verwendung eines Prozessgasgemisches aus Azethylen, Kohlendioxid, Lachgas und Argon, welches in der ersten Zone bei der Plasmaquelle oder bei der ersten Plasmaquelle eingeführt wird. In der zweiten Zone bzw. der zweiten Plasmaquelle wird das Gasgemisch Azethylen, Kohlendioxid und Argon eingeführt, um die Oberschicht zu erzeugen. Mit einem Druckbereich von 0.01 bis 320 mbar und einem Leistungsbereich von 60 bis 2000 Watt wurden so auf den Substraten Polyester, Polypropylen und Polyethylen Oberflächenspannungen von 54 bis 75 mN/m erreicht, welche einen polaren Anteil von 23 bis 51 mN/m aufweisen und mit einem Sauerstoff zu Kohlenstoff Verhältnis von 0.3 bis 0.5 und einem Carboxyl- zu Carbonylgruppen Verhältnis von 0.2 bis 1.2 charakterisiert sind. Die Oberflächenspannung kann unter anderem auch über die Vorschubgeschwindigkeit gesteuert werden. Das Verhältnis Sauerstoff zu Kohlenstoff und das Verhältnis der Carboxyl- zu Carbonyl-Gruppen in den obersten Atomlagen der abgeschiedenen Schichten wurde mit der oberflächenempfindlichen XPS (Photoelektronen Spektroskopie) ermittelt.A thin underlayer 14 is deposited on a substrate 12 with a 2.45 GHz microwave source using a process gas mixture of ethylene, carbon dioxide, nitrous oxide and argon introduced in the first zone at the plasma source or at the first plasma source. In the second zone or the second plasma source, the gas mixture of acetylene, carbon dioxide and argon is introduced to produce the top layer. With a pressure range of 0.01 to 320 mbar and a power range of 60 to 2000 watts, polyester, polypropylene were used on the substrates and polyethylene surface tensions of 54 to 75 mN / m, which have a polar fraction of 23 to 51 mN / m and are characterized with an oxygen to carbon ratio of 0.3 to 0.5 and a carboxyl to carbonyl groups ratio of 0.2 to 1.2. Among other things, the surface tension can be controlled by the feed rate. The oxygen to carbon ratio and the ratio of carboxyl to carbonyl groups in the top atomic layers of the deposited layers were determined by surface-sensitive XPS (photoelectron spectroscopy).

Die gleichen Schichteigenschaften können auch mit allen anderen Entladungsarten mit jeweils Anregungsfrequenzen von Null bis 20 GHz und jeweils mit oder ohne Magnetfeldunterstützung erreicht werden. Beispielhaft erwähnt werden DBDs (Dielectric Barrier Discharges), Niederdruck bis Atmosphärendruck-Glimmentladungen, APNEDs (Atmospheric Pressure Non-Equilibrium Discharges), Surface Discharges, Plasmadüsen und Plasmabreitstrahlbrenner.The same layer properties can also be achieved with all other types of discharge, each with excitation frequencies from zero to 20 GHz and in each case with or without magnetic field support. Exemplary are DBDs (Dielectric Barrier Discharges), low pressure to atmospheric pressure glow discharges, atmospheric pressure non-equilibrium Discharges (APNEDs), surface dicarges, plasma jets and plasma jet burners.

Claims (14)

  1. Process for coating substrates (12) with a polar plasma-polymerised coating of thickness (d) in the nanometre range having long-term stability and multifunctional properties, wherein the process gas contains at least one optionally substituted hydrocarbon compound and at least one inorganic gas,
    characterised in that coating is performed
    - in a first zone or stage with process gases containing at least one hydrocarbon compound, at least one hydrocarbon compound having nitrogen-containing or nitrogen- and oxygen-containing functional groups and/or at least one nitrogen-containing or nitrogen- and oxygen-containing inorganic gas,
    - in a second zone or stage with nitrogen-free process gases containing at least one hydrocarbon compound, at least one hydrocarbon compound having oxygen-containing functional groups and/or at least one oxygen-containing inorganic gas.
  2. Process according to claim 1, characterised in that coating is performed with a process pressure (p) of 10-3 ≤ p ≤ 1000 mbar, preferably 0.1 ≤ p ≤ 500 mbar.
  3. Process according to claim 1 or 2, characterised in that coating is performed with process gases which contain hydrocarbon compounds having up to a maximum of eight C atoms as organic components and oxygen, nitrogen, hydrogen, carbon dioxide, carbon monoxide, nitrogen oxides, ammonia, at least one halogen and/or at least one noble gas as inorganic components.
  4. Process according to one of claims 1 to 3, characterised in that the undercoat and/or topcoat (14, 16) are deposited with additional silicon-containing process gases.
  5. Process according to one of claims 1 to 4, characterised in that coating is performed with a process gas containing aliphatic, alicyclic and/or aromatic hydrocarbon compounds, preferably having functional polar groups such as hydroxyl, carbonyl, carboxylic acid, carboxylic ester, amine, imine, amide and/or conjugated nitrile groups.
  6. Process according to one of claims 1 to 5, characterised in that the nitrogen-containing or nitrogen- and oxygen-containing undercoat (14) is applied with a first plasma source, the oxygen-containing topcoat (16) with a second plasma source, or the undercoat (14) and the topcoat (16) from the same plasma source with process gases introduced in different zones or with alternating process gases.
  7. Coated substrate (10) having at least two multifunctional coats (14, 16) deposited by means of plasma polymerisation and consisting of hydrocarbon compounds,
    characterised in that a plasma-polymerised polar coat (14, 16) in the nanometre range is applied as a nitrogen-containing undercoat (14) applied to the substrate (12) and a nitrogen-free, oxygen-containing polar topcoat (16) applied on top.
  8. Coated substrate (10) according to claim 7, characterised in that the nitrogen-containing or nitrogen- and oxygen-containing undercoat (14) makes up a proportion of 40 to 90%, in particular about 50%, of the total coating thickness (d) and the topcoat (16) makes up a proportion of 60 to 10%, in particular about 50%, of the total coating thickness (d), the coating thickness being preferably 1 to 100 nm.
  9. Coated substrate (10) according to claim 7 or 8, characterised in that the nitrogen/carbon and/or the oxygen/carbon ratio in the plasma-polymerised polar coating (14, 16) consisting of substituted hydrocarbon compounds is in the range from 0.03 to 0.8 and the nitrogen/carbon ratio in the undercoat (14) is in the same range.
  10. Coated substrate (10) according to one of claims 7 to 9, characterised in that the polar topcoat (16), taken as an average in the uppermost approximately 2 nm, has a carbon/oxygen ratio of 0.2 to 0.6, preferably 0.3 to 0.5, and a permanent surface tension of preferably at least 50 mN/m.
  11. Coated substrate (10) according to one of claims 7 to 10, characterised in that it can be welded even with the plasma-polymerised polar coating (14, 16).
  12. Use of the coated substrate (10) according to one of claims 7 to 11 as an anchoring coating (14, 16) for any polar material or any substance, as food packaging or as an antifogging coating.
  13. Use of the coated substrate (10) according to claim 12 for an antifogging coating, particularly in the food sector.
  14. Use of the coated substrate (10) according to claim 12 as a protective coating to prevent migration to the surface, as a barrier with double-sided activity for gases, additives and liquids, as an anti-degradation coating and/or a scratch protection coating.
EP20030813057 2002-12-17 2003-12-17 Substrate comprising a polar plasma-polymerised coating Expired - Lifetime EP1581347B1 (en)

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