WO1996025243A1 - Process for producing a layer system on substrates and the layer system produced by the said method - Google Patents

Process for producing a layer system on substrates and the layer system produced by the said method Download PDF

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Publication number
WO1996025243A1
WO1996025243A1 PCT/DE1996/000277 DE9600277W WO9625243A1 WO 1996025243 A1 WO1996025243 A1 WO 1996025243A1 DE 9600277 W DE9600277 W DE 9600277W WO 9625243 A1 WO9625243 A1 WO 9625243A1
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WIPO (PCT)
Prior art keywords
layer system
layer
metal
substrate
adhesive layer
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Application number
PCT/DE1996/000277
Other languages
German (de)
French (fr)
Inventor
Andreas Weber
Rudolf Thyen
Andreas Dietz
Iris Traus
Claus-Peter Klages
Original Assignee
Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
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Publication of WO1996025243A1 publication Critical patent/WO1996025243A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/02—Apparatus or processes specially adapted for manufacturing resistors adapted for manufacturing resistors with envelope or housing

Definitions

  • the invention relates to a method for producing a layer system consisting of an adhesive layer and an organic coating, in which the adhesive layer is applied by means of barrier discharge and then the substrate coated in this way is then provided with an organic coating, and the layer systems produced using this method .
  • Chromate layers are applied to a large extent on metallic workpieces, preferably galvanized steel workpieces, in particular sheet metal and aluminum. These increase the corrosion resistance of the zinc or aluminum and at the same time serve as a primer for a subsequently applied layer of lacquer or adhesive. Iron materials are covered with a phosphating layer for the same reason Mistake. The effect is based on a certain roughening of the surface and a prevention of reactions between the base material and the paint or adhesive.
  • the chromating layer is obtained by treatment with an acidic aqueous solution of Cr (IV) (Practical Galvanotechnik, Eugen G. Leuze Verlag, Saulgau 1984). Hexavalent chromium is characterized by high toxicity and environmental damage. Chromatization is one of the main sources of Cr (IV) in the environment, in addition, considerable quantities fall in part. highly diluted liquid waste from treatment and rinsing baths, which is therefore disposed of with great energy expenditure. Therefore, environmentally friendly alternatives to chromium-free passivation processes are being sought.
  • Protective layers made of lacquer play a major role in the field of electronic components, particularly in the case of thin-film precision resistors. The problem is similar here: if water vapor penetrates through the protective lacquer layer, the metal-containing resistors are corroded by insufficient electrolyte oxidation and change their resistance value. So far this no adhesive layers are used, which limits the possible uses of these resistors under extreme climatic conditions.
  • Siloxane or SiO x layers are also suitable as adhesive layers for lacquers on electronic components.
  • SiO x layers have hitherto been produced by hydrolysis of organosilicon compounds and silicic acid esters, that is to say wet-chemically or by flame pyrolysis of organosilicon compounds (silicoater process®).
  • the parts to be treated are immersed in highly dilute (approx. 2%) solutions of the silicon-containing starting compound in a solvent. Relative to the layer mass applied, large amounts of solvents are therefore necessary.
  • Disadvantages of the silicoater process are the fire hazard inherent in a burner flame, a temperature load of 150 ° C. on the substrates to be coated, and possibly the need for a subsequent wet chemical step to apply a silane coupling agent.
  • the object of the present invention is a method for producing a
  • an adhesive layer can be applied inexpensively to substrates, in particular metal substrates, the adhesive layer being intended to ensure complete adhesion of a coating over the entire surface.
  • the invention is therefore characterized in that the adhesive layer is applied by means of a physical process, namely by means of a plasma process, and the substrate thus coated is subsequently provided with a coating. It is essential in the solution according to the invention that the adhesive layer is produced by means of a barrier discharge becomes. Since the method according to the invention works at or near atmospheric pressure, it is extremely cost-effective.
  • a barrier discharge is understood to mean a silent electrical discharge, as it is e.g. in their characteristics in H. Gobrecht, 0. Meinhardt, F. Hein: On the silent electrical discharge in ozonizers, Ber. Bunsenges. 68 (1964), 55.
  • the invention therefore expressly includes the disclosure content of this document. It is preferred to work in such a way that a pressure range of 0.1 to 1.5 bar and a voltage range of at least 3 kV is maintained. The selection of the voltage depends on the type and size of the system used. According to the invention, the frequency of the alternating field is in the range from 0.05 to 100 kHz.
  • the adhesive layer is produced in such a way that the precursors provided for the adhesive layer to be applied are supplied as gas or as aerosol in a recipient into the gas discharge zone while observing the process conditions described above.
  • All compounds known from the prior art in the field of gas phase deposition can be used as precursors. Examples of these are hydrocarbons, silicon-containing compounds, boron or phosphorus-containing compounds or metal compounds. It has been shown that it is particularly advantageous if the method described above is carried out with metal as the substrate.
  • the metal can be in a variety of forms.
  • the metal can be part of a passive or active electronic component, such as a component of a thin-film precision resistor in flat chip design or a component of a cylindrical thin-film precision resistor.
  • the substrate is an iron material or aluminum. It is preferred if it is in the form of a strip material, plates, profiles or profile tubes. According to the invention, it is also possible for the substrate to be moved while the layer is being built up.
  • the adhesive layers according to the invention can be provided with organic coating lacquers as well as with an adhesive layer and a connection to a second component that immediately follows. With these adhesive connections one could increased resistance to aging, in the case of paints an increased corrosion resistance is found.
  • the invention further relates to a layer system which has been produced by the method described above.
  • the layer system is constructed in such a way that the adhesive layer preferably has a thickness of 0.001 to 10 ⁇ m, particularly preferably a thickness of 0.01 to 0.1 ⁇ m.
  • Particularly suitable substrates for the layer system according to the invention are sheets made of metal, preferably aluminum, steel and galvanized sheet steel, plates made of steel, galvanized steel or aluminum, profiles, profile tubes, wires made of steel, galvanized steel or aluminum. It is particularly preferred in the layer system if the metal is part of an electronic component, such as a thin-film resistor either in a flat chip or in a cylindrical version.
  • FIG. 1 shows the schematic structure in cross section of a device according to the invention for carrying out the method with a fixed substrate
  • the exemplary embodiment of the device for carrying out the method according to FIG. 1 consists of a recipient 1, in which the electrode arrangement consisting of electrode rods 3 arranged in pairs is installed.
  • Aluminum oxide ceramics are used as the dielectric 2.
  • the barrier removal burns in the discharge space 9 between the rod-shaped electrodes 3 on one side and the counter electrode 5, which is simultaneously connected to the substrate 6, on the other side.
  • flat chip precision resistors were provided with a 0.1 ⁇ m thin SiO x layer.
  • oxygen and TMS were introduced between the electrodes 3 via the gas inlet 7.
  • the supplied gases are directed to the substrate 6 by a fan which is connected to the recipient via the connection 8.
  • FIG. 2 shows a further embodiment of a device for carrying out the method according to the invention, which is constructed analogously to FIG. 1, but with the difference that here the substrate 10, which at the same time represents the counter electrode, is in the recipient 1 is mobile.
  • the substrate 10 which at the same time represents the counter electrode, is in the recipient 1 is mobile.
  • this embodiment it is now possible to coat sheets made of metal, preferably aluminum, steel or galvanized steel sheet, as well as profiles, profile tubes or wires.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention concerns a process for producing a layer system, comprising a tie coat and an organic coating of lacquers or adhesives, on a substrate, in which (a) the tie coat is produced by barrier discharge at a pressure of 0.1-1.5 bar and (b) the substrate thus coated is provided with the organic coating.

Description

Verfahren zur Herstellung eines Schichtsystems auf Substraten und das mit diesem Verfahren hergestellte Schichtsystem Method for producing a layer system on substrates and the layer system produced with this method
Die Erfindung betrifft ein Verfahren zur Herstellung eines Schichtsystems, bestehend aus einer Haftschicht und einem organischen Überzug, bei dem die Haft¬ schicht mittels Barriereentladung aufgebracht wird und dann anschließend das so beschichtete Substrat mit einem organischen Überzug versehen wird, und die mit diesem Verfahren hergestellten Schichtsysteme.The invention relates to a method for producing a layer system consisting of an adhesive layer and an organic coating, in which the adhesive layer is applied by means of barrier discharge and then the substrate coated in this way is then provided with an organic coating, and the layer systems produced using this method .
Auf metallische Werkstücke, vorzugsweise verzinkte Stahlwerkstücke, insbesondere Bleche und Aluminium werden heutzutage in großem Umfang Chromatierschich- ten aufgetragen. Diese erhöhen die Korrosionsbestän¬ digkeit des Zinks bzw. Aluminiums und dienen gleich¬ zeitig als Haftgrund für eine nachfolgend aufgetrage- ne Lackschicht oder Klebung. Eisenwerkstoffe werden aus dem gleichen Grund mit einer Phosphatierschicht versehen. Die Wirkung beruht auf einer gewissen Auf¬ rauhung der Oberfläche und einer Verhinderung von Reaktionen zwischen dem Grundwerkstoff und dem An¬ strich bzw. Klebstoff.Chromate layers are applied to a large extent on metallic workpieces, preferably galvanized steel workpieces, in particular sheet metal and aluminum. These increase the corrosion resistance of the zinc or aluminum and at the same time serve as a primer for a subsequently applied layer of lacquer or adhesive. Iron materials are covered with a phosphating layer for the same reason Mistake. The effect is based on a certain roughening of the surface and a prevention of reactions between the base material and the paint or adhesive.
Die Chromatierschicht wird durch Behandeln mit einer sauren wäßrigen Lösung von Cr(IV) erhalten (Prak¬ tische Galvanotechnik, Eugen G. Leuze Verlag, Saulgau 1984) . Sechswertiges Chrom zeichnet sich durch eine hohe Toxizität und Umweltschädlichkeit aus. Die Chro- matierung ist eine der Haupteintragsquellen von Cr(IV) in die Umwelt, außerdem fallen erhebliche Men¬ gen z.T. stark verdünnter und deshalb mit großem Energieaufwand entsorgter flüssiger Abfälle aus Be- handlungs- und Spülbädern an. Deshalb wird nach um¬ weltgerechten Alternativen zu chromfreien Passivie- rungsverfahren gesucht.The chromating layer is obtained by treatment with an acidic aqueous solution of Cr (IV) (Practical Galvanotechnik, Eugen G. Leuze Verlag, Saulgau 1984). Hexavalent chromium is characterized by high toxicity and environmental damage. Chromatization is one of the main sources of Cr (IV) in the environment, in addition, considerable quantities fall in part. highly diluted liquid waste from treatment and rinsing baths, which is therefore disposed of with great energy expenditure. Therefore, environmentally friendly alternatives to chromium-free passivation processes are being sought.
Die für die Phosphatierung (W. Wiederholt: Die chemi- sehe Oberflächenbehandlung von Metallen zum Korro¬ sionsschutz, Eugen G, Leuze Verlag Saulgau, Württ., 1963) von Eisenwerkstoffen eingesetzten Bäder sind toxologisch, nicht aber ökologisch unbedenklich. Auch hier müssen Abwässer soweit aufbereitet werden, daß die gesetzlich festgelegten Grenzwerte nicht über¬ schritten werden.The baths used for the phosphating (W. Repeatedly: The chemical surface treatment of metals for corrosion protection, Eugen G, Leuze Verlag Saulgau, Württ., 1963) of iron materials are toxic, but not ecologically harmless. Here too, waste water has to be treated to such an extent that the legally defined limit values are not exceeded.
Im Bereich der elektronischen Bauelemente spielen Schutzschichten aus Lack eine große Rolle, insbeson- dere bei Dünnschicht-Präzisionswiderständen. Hier ist das Problem ähnlich gelagert: dringt Wasserdampf durch die schützende Lackschicht, so werden die me¬ tallhaltigen Widerstände bei ungenügender Lackhaftung durch elektrolytische Oxidation korrodiert und ändern ihren Widerstandswert. Bislang werden in diesem An- wendungsfall keine Haftschichten eingesetzt, was die Einsatzmöglichkeiten dieser Widerstände unter extre¬ men klimatischen Bedingungen limitiert.Protective layers made of lacquer play a major role in the field of electronic components, particularly in the case of thin-film precision resistors. The problem is similar here: if water vapor penetrates through the protective lacquer layer, the metal-containing resistors are corroded by insufficient electrolyte oxidation and change their resistance value. So far this no adhesive layers are used, which limits the possible uses of these resistors under extreme climatic conditions.
Als Alternativen zu Chromatier- und Phosphatier- schichten bieten sich neben einer Reihe schwermetall¬ haltiger Verfahren die Beschichtung mit Siloxan- Schichten an (Silylierung, Silanisierung) [Bruce R.W.Hinton: Corrosion Prevention and Chromates, the End of an Era?, Metal Fin. 89, (9) 1991, 55 und 89,In addition to a number of processes containing heavy metals, coating with siloxane layers (silylation, silanization) [Bruce RWHinton: Corrosion Prevention and Chromates, the End of an Era ?, Metal Fin. 89, (9) 1991, 55 and 89,
(10) 1991, 15, J.Pietschmann: "Neue" Verbehandlungs- verfahren gegen Filiformkorrosion, Oberfläche & JOT(10) 1991, 15, J.Pietschmann: "New" treatment methods against filiform corrosion, surface & JOT
(11) 1993, 74].(11) 1993, 74].
Siloxan- oder SiOx-Schichten sind auch als Haft¬ schichten für Lacke auf elektronischen Bauelementen geeignet. SiOx-Schichten werden bislang durch Hydro¬ lyse siliciumorganischer Verbindungen und Kieselsäu¬ reestern, also naßchemisch oder durch Flammenpyrolyse siliciumorganischer Verbindungen (Silicoaterverfah- ren®) hergestellt. Bei den beiden naßchemischen Ver¬ fahren werden die zu behandelnden Teile in stark ver¬ dünnte (ca. 2%ige) Lösungen der siliciumhaltigen Aus¬ gangsverbindung in einem Lösemittel getaucht. Relativ zur aufgebrachten Schichtmasse sind also große Mengen an Lösemitteln notwendig. Nachteil des Silicoaterver- fahrens ist die einer Brennerflamme immanente Feuer¬ gefährdung, eine Temperaturbelastung der zu beschich¬ tenden Substrate um 150° C, sowie u.U. die Notwendig- keit eines nachfolgenden naßchemischen Schrittes zum Auftragen eines Silanhaftvermittlerε.Siloxane or SiO x layers are also suitable as adhesive layers for lacquers on electronic components. SiO x layers have hitherto been produced by hydrolysis of organosilicon compounds and silicic acid esters, that is to say wet-chemically or by flame pyrolysis of organosilicon compounds (silicoater process®). In the two wet chemical processes, the parts to be treated are immersed in highly dilute (approx. 2%) solutions of the silicon-containing starting compound in a solvent. Relative to the layer mass applied, large amounts of solvents are therefore necessary. Disadvantages of the silicoater process are the fire hazard inherent in a burner flame, a temperature load of 150 ° C. on the substrates to be coated, and possibly the need for a subsequent wet chemical step to apply a silane coupling agent.
Zusammenfassend ist somit festzustellen, daß alle aus dem Stand der Technik bisher bekannten Verfahren zur Gewährung eines ganzflächigen Korrosionsschutzes ver- fahrensbedingte Nachteile aufweisen. Beim Auftragen von Lacken oder Klebungen ist nämlich dafür Sorge zu tragen, daß an der Grenzfläche ganzflächig ein guter Kontakt zwischen Untergrund und Auflage besteht. Ist dies nicht der Fall, kann das durch die Auflage dif¬ fundierende Wasser an delaminierten Stellen, wo der Kontakt mangelhaft ist, kondensieren. Dies führt langfristig zu einer Korrosion des Grundmaterials unter dem ansonsten intakten Lack bzw. der Klebung. Die Korrosionsschutzwirkung ist also wesentlich von einer ganzflächig perfekten Haftung der Auflage auf dem Untergrund abhängig.In summary, it can thus be stated that all of the methods known to date from the prior art for providing full-surface corrosion protection have driving-related disadvantages. When applying lacquers or adhesives, care must be taken to ensure that there is good contact between the surface and the support over the entire surface at the interface. If this is not the case, the water diffusing due to the support can condense at delaminated points where the contact is poor. In the long term, this leads to corrosion of the base material under the otherwise intact paint or adhesive. The corrosion protection effect is therefore largely dependent on the perfect surface coverage of the support on the surface.
Ausgehend hiervon, ist es die Aufgabe der vorliegen- den Erfindung, ein Verfahren zur Herstellung einesProceeding from this, the object of the present invention is a method for producing a
Schichtsystems und das Schichtsystem selbst zur Ver¬ fügung zu stellen, mit dem kostengünstig eine Haft¬ schicht auf Substrate, insbesondere Metallsubstrate, aufgebracht werden kann, wobei die Haftschicht eine ganzflächige vollständige Haftung eines Überzuges gewährleisten soll.To provide the layer system and the layer system itself, by means of which an adhesive layer can be applied inexpensively to substrates, in particular metal substrates, the adhesive layer being intended to ensure complete adhesion of a coating over the entire surface.
Die Aufgabe wird im Hinblick auf das Verfahren durch die kennzeichnenden Merkmale des Anspruches 1, in be- zug auf das Schichtsystem durch die kennzeichnendenThe object is achieved with regard to the method by the characterizing features of claim 1, in relation to the layer system by the characterizing
Merkmale des Anspruches 8, gelöst. Die Unteransprüche zeigen vorteilhafte Weiterbildungen auf.Features of claim 8 solved. The subclaims show advantageous developments.
Die Erfindung zeichnet sich demnach dadurch aus, daß die Haftschicht mittels eines physikalischen Verfah¬ rens, nämlich mittels eines Plasmaverfahrens, aufge¬ bracht wird und das dann so beschichtete Substrat nachträglich mit einem Überzug versehen wird. Wesent¬ lich bei der erfindungsgemäßen Lösung ist, daß die Haftschicht mittels einer Barriereentladung erzeugt wird. Da das erfindungsgemäße Verfahren bei oder in der Nähe von Atmosphärendruck arbeitet, ist es äu¬ ßerst kostengünstig.The invention is therefore characterized in that the adhesive layer is applied by means of a physical process, namely by means of a plasma process, and the substrate thus coated is subsequently provided with a coating. It is essential in the solution according to the invention that the adhesive layer is produced by means of a barrier discharge becomes. Since the method according to the invention works at or near atmospheric pressure, it is extremely cost-effective.
Erfindungsgemäß wird unter einer Barriereentladung eine stille elektrische Entladung verstanden, wie sie z.B. in ihren Charakteristika in H. Gobrecht, 0. Meinhardt, F. Hein: Über die stille elektrische Ent¬ ladung in Ozonisatoren, Ber. Bunsenges. 68 (1964), 55, beschrieben ist. Die Erfindung schließt deshalb ausdrücklich den Offenbarungsgehalt dieses Dokuments mit ein. Bevorzugt wird dabei so gearbeitet, daß ein Druckbereich von 0,1 bis 1,5 bar und ein Spannungs¬ bereich von minestens 3 kV eingehalten wird. Die Aus- wähl der Spannung richtet sich dabei nach der Art und Größe der verwendeten Anlage. Die Frequenz des Wech¬ selfeldes liegt erfindungsgemäß im Bereich von 0,05 bis 100 kHz.According to the invention, a barrier discharge is understood to mean a silent electrical discharge, as it is e.g. in their characteristics in H. Gobrecht, 0. Meinhardt, F. Hein: On the silent electrical discharge in ozonizers, Ber. Bunsenges. 68 (1964), 55. The invention therefore expressly includes the disclosure content of this document. It is preferred to work in such a way that a pressure range of 0.1 to 1.5 bar and a voltage range of at least 3 kV is maintained. The selection of the voltage depends on the type and size of the system used. According to the invention, the frequency of the alternating field is in the range from 0.05 to 100 kHz.
Zur Herstellung der Haftschicht wird dabei so verfah¬ ren, daß unter Einhaltung der vorstehend beschriebe¬ nen Verfahrensbedingungen in einen Rezipienten in die Gasentladungszone die für die aufzubringende Haft¬ schicht vorgesehenen Prekursoren als Gas oder als Aerosol zugeführt werden. Als Prekursoren können da¬ bei alle aus dem Stand der Technik bisher bekannten Verbindungen aus dem Bereich der Gasphasenabscheidung eingesetzt werden. Beispiele hierfür sind Kohlenwas¬ serstoffe, Siliciu enthaltende Verbindungen, Bor oder Phosphor enthaltende Verbindungen oder Metall¬ verbindungen. Es hat sich gezeigt, daß es ganz beson¬ ders günstig ist, wenn das vorstehend beschriebene Verfahren mit Metall als Substrat durchgeführt wird. Das Metall kann hierbei in vielfältigen Formen vor- liegen. So kann das Metall z.B. ein Bestandteil eines passiven oder aktiven elektronischen Bauteils sein, wie z.B. ein Bestandteil eines Dünnschicht-Präzi¬ sionswiderstandes in Flachchipausführung oder ein Bestandteil eines zylindrischen Dünnschicht-Präzi- sionswiderstandes. Besonders gute Ergebnisse in bezug auf ein ganzflächiges Aufbringen der Haftschicht wur¬ den insbesondere dann erzielt, wenn das Substrat ein Eisenwerkstoff oder Aluminium ist. Bevorzugt ist es, wenn es als Bandmaterial, Platten, Profile oder Pro- filrohre vorliegt. Erfindungsgemäß ist es auch mög¬ lich, daß das Substrat während des Schichtaufbaus bewegt wird.The adhesive layer is produced in such a way that the precursors provided for the adhesive layer to be applied are supplied as gas or as aerosol in a recipient into the gas discharge zone while observing the process conditions described above. All compounds known from the prior art in the field of gas phase deposition can be used as precursors. Examples of these are hydrocarbons, silicon-containing compounds, boron or phosphorus-containing compounds or metal compounds. It has been shown that it is particularly advantageous if the method described above is carried out with metal as the substrate. The metal can be in a variety of forms. For example, the metal can be part of a passive or active electronic component, such as a component of a thin-film precision resistor in flat chip design or a component of a cylindrical thin-film precision resistor. Particularly good results with regard to the application of the adhesive layer over the entire surface were achieved in particular when the substrate is an iron material or aluminum. It is preferred if it is in the form of a strip material, plates, profiles or profile tubes. According to the invention, it is also possible for the substrate to be moved while the layer is being built up.
Die mit dem naßchemischen Verfahren zur Herstellung der Haftschicht (Chromatieren, Phosphatieren, Sily- lieren und Silanisieren) verbundenen Probleme mit flüssigen Abfällen oder Abwässern werden durch das erfindungsgemäße Verfahren, bei dem ja ausschließlich gasförmige Ausgangsverbindungen zugesetzt werden, vermieden. Flüssigkeiten als Lösemittel für die Aus¬ gangsverbindungen sind genauso wenig nötig, wie Bren¬ nergase zur Aufrechterhaltung der Flamme. Die Tempe¬ raturbelastung der Substrate ist damit vernachlässig- bar klein (< als 60° C) , da es sich um ein sog. nichtthermisches Plasma handelt. Besonders überra¬ schend war es, daß durch das erfindungsgemäße Verfah¬ ren nicht nur die vorstehend beschriebenen Nachteile des Standes der Technik beseitigt wurden, sondern daß die Schichten gleichzeitig zu einer Haftverbesserung mit dem Überzug führen. Es hat sich dabei gezeigt, daß die erfindungsgemäßen Haftschichten sowohl mit organischen Überzugslacken versehen werden können, wie auch mit einer Klebeschicht und einem unmittelbar sich daran anschließenden Verbinden mit einem zweiten Bauteil. Bei diesen Klebeverbindungen konnte eine erhöhte Alterungsbeständigkeit, bei den Anstrichen eine erhöhte Korrosionsbeständigkeit festgestellt werden.The problems with liquid waste or waste water associated with the wet chemical process for producing the adhesive layer (chromating, phosphating, silylating and silanizing) are avoided by the process according to the invention, in which only gaseous starting compounds are added. Liquids as solvents for the starting compounds are just as unnecessary as burner gases for maintaining the flame. The temperature load on the substrates is therefore negligibly small (<than 60 ° C.), since it is a so-called non-thermal plasma. It was particularly surprising that the process according to the invention not only eliminated the disadvantages of the prior art described above, but also that the layers simultaneously improve the adhesion with the coating. It has been shown that the adhesive layers according to the invention can be provided with organic coating lacquers as well as with an adhesive layer and a connection to a second component that immediately follows. With these adhesive connections one could increased resistance to aging, in the case of paints an increased corrosion resistance is found.
Die Erfindung betrifft weiterhin ein Schichtsystem, das nach dem vorstehend beschriebenen Verfahren her¬ gestellt worden ist. Das Schichtsystem ist dabei so aufgebaut, daß die Haftschicht bevorzugt eine Dicke von 0,001 bis 10 μm, besonders bevorzugt eine Dicke von 0,01 bis 0,1 μm, hat. Als Substrate für das er¬ findungsgemäße Schichtsystem eigenen sich ganz beson¬ ders Bahnen aus Metall, vorzugsweise Aluminium, Stahl und verzinktes Stahlblech, Platten aus Stahl, ver¬ zinktem Stahl oder Aluminium, Profile, Profilrohre, Drähte aus Stahl, verzinktem Stahl oder Aluminium. Besonders bevorzugt ist es bei dem Schichtsystem, wenn das Metall ein Bestandteil eines elektronischen Bauteils ist, wie z.B. ein Dünnschichtwiderstand so¬ wohl in Flachchip oder auch in zylindrischer Ausfüh- rung.The invention further relates to a layer system which has been produced by the method described above. The layer system is constructed in such a way that the adhesive layer preferably has a thickness of 0.001 to 10 μm, particularly preferably a thickness of 0.01 to 0.1 μm. Particularly suitable substrates for the layer system according to the invention are sheets made of metal, preferably aluminum, steel and galvanized sheet steel, plates made of steel, galvanized steel or aluminum, profiles, profile tubes, wires made of steel, galvanized steel or aluminum. It is particularly preferred in the layer system if the metal is part of an electronic component, such as a thin-film resistor either in a flat chip or in a cylindrical version.
Weitere Merkmale, Einzelheiten und Vorzüge der Erfin¬ dung ergeben sich aus der folgenden Beschreibung zweier Ausführungsformen und eines Beispieles. Hier- bei zeigen:Further features, details and advantages of the invention result from the following description of two embodiments and an example. Show here:
Figur 1 den schematischen Aufbau im Querschnitt einer erfin¬ dungsgemäßen Vorrichtung zur Durchführung des Verfah- rens mit einem feststehenden Substrat,FIG. 1 shows the schematic structure in cross section of a device according to the invention for carrying out the method with a fixed substrate,
Figur 2 eine Vorrichtung gemäß Figur 1, jedoch mit einem be¬ weglichen Substrat. Die beispielhafte Ausführungsform der Vorrichtung zur Durchführung des Verfahrens gemäß Fig. 1 besteht aus einem Rezipienten 1, in dem die aus paarweise ange¬ ordneten Elektrodenstäben 3 bestehende Elektrodenan- Ordnung eingebaut ist. Als Dielektrikum 2 werden Alu¬ miniumoxidkeramiken verwendet. Die Barriereentlandung brennt im Entladungsraum 9 zwischen den stabförmigen Elektroden 3 auf der einen und der Gegenelektrode 5, die gleichzeitig mit dem Substrat 6 verbunden ist, auf der anderen Seite. Bei der Ausführungsform nach Fig. 1 wurden Flachchippräzisionswiderstände mit ei¬ ner 0,1 μm dünnen SiOx-Schicht versehen. Dazu wurden Sauerstoff und TMS über den Gaseinlaß 7 zwischen den Elektroden 3 eingeleitet. Die zugeführten Gase erfuh- ren durch ein Gebläse, das über den Anschluß 8 an den Rezipienten angeschlossen ist, eine gezielte Konvek- tion auf das Substrat 6 hin. Unter der Einwirkung der Barriereentladung zersetzen sich die Ausgangsverbin¬ dungen unter Bildung der Haftschicht. Die so be- schichteten Widerstände wurden anschließend mit Lack als Überzug versehen. Im Klimatest konnte dabei eine erhöhte Korrosionsbeständigkeit gegenüber den nicht mit der Haftschicht versehenen Referenzproben nach¬ gewiesen werden. Das erfindungsgemäße Verfahren ist dabei grundsätzlich mit allen aus dem Stand der Tech¬ nik bekannten Überzügen kombinierbar. Derartige Über¬ züge sind z.B. Schutzlacke mit diffusionshemmender Wirkung, Schutzlacke mit Dekofunktion, Farben, Druck¬ farben, Kleber. In dem Ausführungsbeispiel nach Fig. 1 wurden folgenden Prozeßparamter eingehalten: Prozeßparameter:2 shows a device according to FIG. 1, but with a movable substrate. The exemplary embodiment of the device for carrying out the method according to FIG. 1 consists of a recipient 1, in which the electrode arrangement consisting of electrode rods 3 arranged in pairs is installed. Aluminum oxide ceramics are used as the dielectric 2. The barrier removal burns in the discharge space 9 between the rod-shaped electrodes 3 on one side and the counter electrode 5, which is simultaneously connected to the substrate 6, on the other side. In the embodiment according to FIG. 1, flat chip precision resistors were provided with a 0.1 μm thin SiO x layer. For this purpose, oxygen and TMS were introduced between the electrodes 3 via the gas inlet 7. The supplied gases are directed to the substrate 6 by a fan which is connected to the recipient via the connection 8. Under the action of the barrier discharge, the starting compounds decompose to form the adhesive layer. The resistors coated in this way were then coated with lacquer. In the climate test, it was possible to demonstrate increased corrosion resistance compared to the reference samples not provided with the adhesive layer. The method according to the invention can in principle be combined with all coatings known from the prior art. Such coatings are, for example, protective lacquers with a diffusion-inhibiting effect, protective lacquers with a decorative function, paints, printing inks and adhesives. The following process parameters were adhered to in the exemplary embodiment according to FIG. 1: Process parameters:
Spannung: 7,5 kVVoltage: 7.5 kV
Frequenz des Wechselfeldes: 40 kHzFrequency of the alternating field: 40 kHz
Zahl der Dielektrika pro Entladungsspalt: 1 aus Aluminiumoxidkeramik Druck in der Behandlungskammer: 1.000 mbar Schicht: SiOx, hergestellt aus Tetramethylsilan (TMS) und SauerstoffNumber of dielectrics per discharge gap: 1 made of aluminum oxide ceramic Pressure in the treatment chamber: 1,000 mbar layer: SiO x , made from tetramethylsilane (TMS) and oxygen
Gasflüsse: Sauerstoff: 1.000 sccm (Standard-Ku- bikcentimeter pro Minute) TMS: 100 sccmGas flows: Oxygen: 1,000 sccm (standard cubic centimeters per minute) TMS: 100 sccm
Substrat: FlachchippräzisionswiderständeSubstrate: flat chip precision resistors
Fig. 2 zeigt eine weitere Ausführungsform einer Vor¬ richtung zur Durchführung des erfindungsgemäßen Ver- fahrens, die analog Fig. 1 aufgebaut ist, jedoch mit dem Unterschied, daß hier das Substrat 10, das ja gleichzeitig die Gegenelektrode darstellt, im Rezi- pieten 1 beweglich ist. Durch diese Ausgestaltungs¬ form ist es nun möglich, Bahnen aus Metall, vorzugs- weise Aluminium, Stahl oder verzinktem Stahlblech sowie Profile, Profilrohre oder Drähte zu be¬ schichten. FIG. 2 shows a further embodiment of a device for carrying out the method according to the invention, which is constructed analogously to FIG. 1, but with the difference that here the substrate 10, which at the same time represents the counter electrode, is in the recipient 1 is mobile. With this embodiment it is now possible to coat sheets made of metal, preferably aluminum, steel or galvanized steel sheet, as well as profiles, profile tubes or wires.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung eines Schichtsystems, bestehend aus einer Haftschicht und einem orga- nischen Überzug, wie Lacke oder Klebstoffe, auf einem Substrat, dadurch gekennzeichnet, daß1. A process for producing a layer system consisting of an adhesive layer and an organic coating, such as lacquers or adhesives, on a substrate, characterized in that
a) die Haftschicht mittels einer Barriereentla- düng bei einem Druck von 0,1 bis 1,5 bar erzeugt wird unda) the adhesive layer is produced by means of a barrier discharge at a pressure of 0.1 to 1.5 bar and
b) daß das so beschichtete Substrat mit dem or¬ ganischen Überzug versehen wird.b) that the substrate coated in this way is provided with the organic coating.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß mit einer Spannung von mindestens 3 kV gearbeitet wird.2. The method according to claim 1, characterized in that one works with a voltage of at least 3 kV.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß mit einer Frequenz des Wechselfeldes im Bereich von 0,05 bis 100 kHz gearbeitet wird.3. The method according to claim 1 or 2, characterized in that one works with a frequency of the alternating field in the range of 0.05 to 100 kHz.
4. Verfahren nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß in die Gasentla¬ dungszone die für die aufzubringende Haftschicht eingesetzen Prekursoren als Gas oder als Aerosol zugeführt werden. 4. The method according to at least one of claims 1 to 3, characterized in that the precursors used for the adhesive layer to be applied are supplied as gas or as aerosol into the gas discharge zone.
5. Verfahren nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß als Prekursoren Ver¬ bindungen eingesetzt werden, die aus der Gruppe Kohlenwasserstoffe, Silicium enthaltende Verbin¬ dungen, Bor oder Phosphor enthaltende Verbindun¬ gen, Metallverbindungen, ausgewählt werden.5. The method according to at least one of claims 1 to 4, characterized in that compounds are used as precursors which are selected from the group consisting of hydrocarbons, silicon-containing compounds, boron or phosphorus-containing compounds, metal compounds.
6. Verfahren nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß als Substrat Metall eingesetzt wird.6. The method according to at least one of claims 1 to 5, characterized in that metal is used as the substrate.
7. Verf hren nach mindestens einem der Ansprüche l bis 6, dadurch gekennzeichnet, daß das Substrat während der Schichtbildung bewegt wird.7. The method according to at least one of claims 1 to 6, characterized in that the substrate is moved during the layer formation.
8. Schichtsystem auf Substraten, hergestellt nach mindestens einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Schichtdicke der Haftschicht im Bereich von 0,001 bis 10 μm liegt.8. layer system on substrates, produced according to at least one of claims 1 to 7, characterized in that the layer thickness of the adhesive layer is in the range of 0.001 to 10 microns.
9. Schichtsystem nach Anspruch 8, dadurch gekennzeichnet, daß die Schichtdicke im Bereich von 0,01 bis 0,1 μm liegt.9. Layer system according to claim 8, characterized in that the layer thickness is in the range of 0.01 to 0.1 microns.
10. Schichsystem nach Anspruch 8 oder 9, dadurch gekennzeichnet, daß das Metall ein Be¬ standteil eines passiven oder aktiven elektroni¬ schen Bauteils ist. 10. Layer system according to claim 8 or 9, characterized in that the metal is a component of a passive or active electronic component.
11. Schichtsystem nach Anspruch 8 oder 9, dadurch gekennzeichnet, daß das Metall ein Be¬ standteil eines Dünnschichtpräzisionswiderstands in Flachchipausführung ist.11. Layer system according to claim 8 or 9, characterized in that the metal is a component of a thin-film precision resistor in flat chip design.
12. Schichtsystem nach Anspruch 8 oder 9, dadurch gekennzeichnet, daß das Metall ein Be¬ standteil eines zylindrischen Dünnschichtpräzi- sionswiderstandes ist.12. Layer system according to claim 8 or 9, characterized in that the metal is a component of a cylindrical thin-film precision resistor.
13. Schichtsystem nach Anspruch 8 oder 9, dadurch gekennzeichnet, daß das Metall ein Ei¬ senwerkstoff ist, wie z.B. Stahl oder verzinkter Stahl, oder Aluminium ist.13. Layer system according to claim 8 or 9, characterized in that the metal is an iron material, such as e.g. Steel or galvanized steel, or aluminum.
14. Schichtsystem nach Anspruch 13, dadurch gekennzeichnet, daß das Metall in Form von Bandmaterial, Platten, Profilen, Profilroh¬ ren oder Drähten vorliegt. 14. Layer system according to claim 13, characterized in that the metal is in the form of strip material, plates, profiles, Profilroh¬ ren or wires.
PCT/DE1996/000277 1995-02-17 1996-02-16 Process for producing a layer system on substrates and the layer system produced by the said method WO1996025243A1 (en)

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