WO2003014232A1 - Material for producing abrasion-proof, hydrophobic and/or oleophobic coatings - Google Patents

Material for producing abrasion-proof, hydrophobic and/or oleophobic coatings Download PDF

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Publication number
WO2003014232A1
WO2003014232A1 PCT/DE2002/002667 DE0202667W WO03014232A1 WO 2003014232 A1 WO2003014232 A1 WO 2003014232A1 DE 0202667 W DE0202667 W DE 0202667W WO 03014232 A1 WO03014232 A1 WO 03014232A1
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Prior art keywords
substrate
acid
hydrophobic
temperature
material according
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PCT/DE2002/002667
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German (de)
French (fr)
Inventor
Stefan Sepeur
Frank Gross
Jan Interwies
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Nano-X Gmbh
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Publication of WO2003014232A1 publication Critical patent/WO2003014232A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
    • C04B41/4933—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane containing halogens, i.e. organohalogen silanes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
    • C04B41/4977—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers characterised by the number of silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/82—Coating or impregnation with organic materials
    • C04B41/84—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/76—Hydrophobic and oleophobic coatings

Definitions

  • the present invention relates to a material for producing abrasion-resistant, hydrophobic and / or oleophobic coatings and their use.
  • EP 0 109 171 discloses fluorocarbon resins or generally fluorochemical copolymers and cardboards and textile fibers coated therewith.
  • the coating materials known from the prior art at least partially have a comparatively good water, oil and / or dirt-repellent effect, they are still in need of improvement. Improvements are possible, in particular with regard to the abrasion resistance and chemical resistance that can be achieved. This is particularly important in the areas in which the coating materials are to be used for coating ceramic floor tiles or chrome surfaces in the sanitary area.
  • the surfaces coated with the coating materials known from the prior art frequently also show a loss of the hydrophobic effect in the strongly basic medium.
  • the present object is achieved by a material with the features of claim 1 and a use with the features of claim 6.
  • a hydrophobic and / or oleophobic group is understood to mean a branched or unbranched alkyl and / or polyfluoroalkyl and / or perfluoroalkyl group. These groups can be straight-chain or branched or can also contain saturated, unsaturated or aromatic cyclic groups.
  • the hydrophobic and / or oleophobic groups can furthermore have substituents, the substituents preferably having functionalities which later crosslink e.g. enable by UV or heat-induced polymerization reactions. Examples of such substituents are generally substituents e.g. with vinyl groups or the like. Moreover, such groups capable of crosslinking are familiar to the person skilled in the art from the prior art mentioned at the beginning.
  • the abrasion resistance of coatings which are produced from the material according to the invention and are based on silanes with hydrophobic and / or oleophobic groups is increased because it has previously been assumed that longer chain lengths are used for the hydrophobic and / or oleophobic groups tend to reduce abrasion resistance. It is preferred if the chain length of the at least one alkyl group contained in the corresponding silane and / or polyfluoroalkyl and / or perfluoroalkyl group is between 10 and 30 carbon atoms, a chain length of 12 to 20 carbon atoms being particularly preferred on account of the availability of the corresponding starting compounds and the ease of handling.
  • the material according to the invention for producing abrasion-resistant hydrophobic and / or oleophobic coatings generally contains the abovementioned silane in a solvent and / or emulsifier. Due to economic, ecological and procedural conditions, it is preferred if this solvent and / or emulsifying agent is water or at least has a high water content. Aqueous solutions of alcohols such as ethanol, methanol, propanol, isopropanol and / or butanol (in all its isomeric forms) are therefore also particularly good as solvents and / or emulsifiers and thus as a constituent of the material according to the invention for producing abrasion-resistant, hydrophobic and / or oleophobic coatings.
  • alcohols such as ethanol, methanol, propanol, isopropanol and / or butanol (in all its isomeric forms) are therefore also particularly good as solvents and / or emulsifiers and thus as
  • the material for producing abrasion-resistant, hydrophobic and / or oleophobic coatings furthermore contains a compound which acts as an activator on the silane contained in the material and already described, which is in particular an alkoxysilane. It is preferred if this compound is an acid which, by protonating the oxygen of the alkoxy group, accelerates the hydrolytic cleavage of the alkoxide group. Essentially methoxy groups and ethoxy groups are used as alkoxide groups and the hydrolytic cleavage of the alkoxide group can be controlled via the acid strength of the acid used as activator. It is particularly preferred if the acid used as an activator is an inorganic acid or an organic acid, ie in particular HCl, H 2 SO 4 and H 3 PO 4 and acetic or formic acid
  • the material according to the invention has a very wide range of applications. Almost all known natural and synthetic substrates can be coated with the material according to the invention with the formation of wear-resistant hydrophobic and / or oleophobic coatings. It is therefore preferred if the substrate is a glass-like and / or ceramic substrate (e.g. glass, ceramic, enamel), a textile (e.g. Curtain fabric, awning fabric, clothing fabric), a fiber, leather, wood, a metal (e.g. chrome, brass, copper, zinc, stainless steel), a plastic, paper, cardboard or a natural material.
  • a glass-like and / or ceramic substrate e.g. glass, ceramic, enamel
  • a textile e.g. Curtain fabric, awning fabric, clothing fabric
  • a fiber leather, wood, a metal (e.g. chrome, brass, copper, zinc, stainless steel), a plastic, paper, cardboard or a natural material.
  • the surface of the same is applied during the application of the coating, i.e. has at least room temperature during the application of the material according to the invention for producing abrasion-resistant, hydrophobic and / or oleophobic coatings.
  • the temperature for carrying out such a coating is in the range from about room temperature to about 400 ° C., preferably in the range from 40 to 200 ° C. and particularly preferably in the range from 60 to 170 ° C.
  • the preferred temperature ranges for the application of the coating result the temperature resistance of the silanes preferably used in the material according to the invention and / or the substrates to be coated.
  • the level of the temperature when applying the material according to the invention is of particular importance for the layer formation, since it determines the drying rate, i.e. affects the rate at which the solvent and / or emulsifier is removed.
  • the material according to the invention can furthermore be applied to the substrate by any coating method known to the person skilled in the art, it preferably being carried out by pouring, flooding, dipping or spinning and particularly preferably by spraying.
  • post-annealing it is advantageous if after the application of the material according to the invention so-called post-annealing takes place.
  • heat is further supplied to the substrate, advantageously in such a way that the substrate temperature is maintained. This not only enables drying, but also cross-linking of the molecules within the coating, depending on the selected conditions and the silanes used.
  • the preparation of the silanes intended for use in the material according to the invention, in particular trialkoxysilanes, is generally familiar to the person skilled in the art, so that a Description of the manufacturing process can be omitted here.
  • the coating of, for example, a sanitary ware is generally carried out as follows.

Abstract

The invention relates to a material for producing abrasion-proof, hydrophobic and/or oleophobic coatings which is characterized by containing at least one alkoxysilane having at least one alkyl and/or polyfluoroalkyl and/or perfluoroalkyl group having a chain length of at least 20 carbon atoms.

Description

Material zur Herstellung abriebfester, hydrophober und/oder oleophober Beschichtungen Material for the production of abrasion-resistant, hydrophobic and / or oleophobic coatings
Die vorliegende Erfindung betrifft ein Material zur Herstellung abriebfester, hydrophober und/oder oleophober Beschichtungen und deren Verwendung.The present invention relates to a material for producing abrasion-resistant, hydrophobic and / or oleophobic coatings and their use.
Im Stand der Technik sind hydrophobe und/oleophobe Beschichtungsmaterialien sowohl auf der Basis von Fluorverbindungen (Fluorsilane, Fluorcarbonharze, Fluoracrylate etc.) als auch auf Silikonbasis beschrieben. Das US-Patent 5,274,159 offenbart zersetzbare, fluorierte Alkoxysilantenside, die wenigstens eine hydrolytisch abspaltbare Gruppe aufweisen und daraus hergestellte wasser- und ölabstoßende Schichten. Die EP 0587 667 beschreibt fluorhaltige anorganische Polykondensate und deren Herstellung sowie Verwendung zur Beschichtung von Substraten. Die DE 196 49 954 sowie 196 49 955 betreffen im Grunde das gleiche technische Gebiet, gehen aber von zum Teil recht kompliziert und komplex aufgebauten Verbindungen aus.The prior art describes hydrophobic and / oleophobic coating materials both on the basis of fluorine compounds (fluorosilanes, fluorocarbon resins, fluoroacrylates etc.) and on a silicone basis. US Pat. No. 5,274,159 discloses decomposable, fluorinated alkoxysilane surfactants which have at least one hydrolytically removable group and water- and oil-repellent layers produced therefrom. EP 0587 667 describes fluorine-containing inorganic polycondensates and their production and use for coating substrates. DE 196 49 954 and 196 49 955 basically relate to the same technical field, but assume that connections are sometimes quite complicated and complex.
Während die vorgenannten Dokumente aus dem Stand der Technik allgemein Fluorsilanhydrosilate bzw. -kondensate betreffen, offenbart die EP 0 109 171 Fluorcarbonharze oder allgemein fluorchemische Copolymere und damit beschichtete Pappen und Textilfasern.While the aforementioned documents from the prior art generally relate to fluorosilane hydrosilates or condensates, EP 0 109 171 discloses fluorocarbon resins or generally fluorochemical copolymers and cardboards and textile fibers coated therewith.
Obwohl die aus dem Stand der Technik bekannten Beschichtungsmaterialien zumindest teilweise Ober eine vergleichsweise gute wasser-, öl- und/oder schmutzabweisende Wirkung verfugen, sind sie immer noch verbesserungswürdig. Insbesondere hinsichtlich der erzielbaren Abriebfestigkeiten und Chemikalienbeständigkeiten sind Verbesserungen möglich. Dies ist insbesondere auf den Gebieten von besonderer Bedeutung, auf denen die Beschichtungsmaterialien zur Beschichtung von keramischen Bodenfliesen oder von Chromoberflächen im Sanitärbereich eingesetzt werden sollen. Die mit den aus dem Stand der Technik bekannten Beschichtungsmaterialien beschichteten Oberflächen zeigen weiterhin häufig einen Verlust des hydrophoben Effekts im stark basischen Medium.Although the coating materials known from the prior art at least partially have a comparatively good water, oil and / or dirt-repellent effect, they are still in need of improvement. Improvements are possible, in particular with regard to the abrasion resistance and chemical resistance that can be achieved. This is particularly important in the areas in which the coating materials are to be used for coating ceramic floor tiles or chrome surfaces in the sanitary area. The surfaces coated with the coating materials known from the prior art frequently also show a loss of the hydrophobic effect in the strongly basic medium.
Es ist daher Aufgabe der vorliegenden Erfindung das eingangs erwähnte Material dahingehend weiterzubilden, daß es zumindest einen Teil der aus dem Stand der Technik bekannten Nachteile vermeidet. In ihrer grundlegendsten Form besteht die der vorliegenden Erfindung zugrundliegenden Aufgabe in der Bereitstellung wenigstens eines weiteren Materials zur Herstellung abriebfester, hydrophober und/oder oleophober Beschichtungen.It is therefore an object of the present invention to develop the material mentioned at the outset in such a way that it avoids at least some of the disadvantages known from the prior art. In its most basic form is that of the present invention underlying task in the provision of at least one further material for producing abrasion-resistant, hydrophobic and / or oleophobic coatings.
Weiterhin ist es Aufgabe der vorliegenden Erfindung eine Verwendung des Materials zur Herstellung abriebfester, hydrophober und/oder oleophober Beschichtungen anzugeben.Furthermore, it is an object of the present invention to provide a use of the material for producing abrasion-resistant, hydrophobic and / or oleophobic coatings.
Die vorliegende Aufgabe wird durch ein Material mit den Merkmalen des Anspruchs 1 sowie einer Verwendung mit den Merkmalen des Anspruchs 6 gelöst.The present object is achieved by a material with the features of claim 1 and a use with the features of claim 6.
Vorteilhafte Ausgestaltungen der Erfindung sind jeweils Gegenstand der Ansprüche 2 bis 5 sowie 7 bis 10.Advantageous embodiments of the invention are the subject matter of claims 2 to 5 and 7 to 10, respectively.
Überraschend hat sich gezeigt, daß der Einsatz von Silanen mit hydrophoben und/oder oleophoben Gruppen mit einer Kettenlänge von wenigstens 10 Kohlenstoffatomen zu einer deutlich höheren Abrieb- und Chemikalienbeständigkeit der mit diesen Silanen hergestellten Beschichtungen führt. Als hydrophobe und/oder oleophobe Gruppe wird eine verzweigte oder nicht verzweigte Alkyl- und/oder Polyfluoralkyl- und/oder Perfluoralkyl-Gruppe verstanden. Diese Gruppierungen können gradkettig oder verzweigt sein oder auch gesättigte, ungesättigte oder aromatische cyclische Gruppierungen enthalten. Die hydrophoben und/oder oleophoben Gruppen können weiterhin Substituenten aufweisen, wobei die Substituenten bevorzugt Funktionalitäten aufweisen, die eine spätere Vernetzung z.B. durch UV- oder wärmeinduzierte Polymerisationsreaktionen ermöglichen. Als Beispiel für derartige Substituenten sind allgemein Substituenten z.B. mit Vinylgruppen oder dergl. zu nennen. Im übrigen sind derartige zur Vernetzung fähige Gruppen dem Fachmann aus dem eingangs erwähnten Stand der Technik geläufig.Surprisingly, it has been shown that the use of silanes with hydrophobic and / or oleophobic groups with a chain length of at least 10 carbon atoms leads to a significantly higher abrasion and chemical resistance of the coatings produced with these silanes. A hydrophobic and / or oleophobic group is understood to mean a branched or unbranched alkyl and / or polyfluoroalkyl and / or perfluoroalkyl group. These groups can be straight-chain or branched or can also contain saturated, unsaturated or aromatic cyclic groups. The hydrophobic and / or oleophobic groups can furthermore have substituents, the substituents preferably having functionalities which later crosslink e.g. enable by UV or heat-induced polymerization reactions. Examples of such substituents are generally substituents e.g. with vinyl groups or the like. Moreover, such groups capable of crosslinking are familiar to the person skilled in the art from the prior art mentioned at the beginning.
Es ist insbesondere für den Fachmann überraschend, daß die Abriebfestigkeit von Beschichtungen, die aus dem erfindungsgemäßen Material hergestellt sind und auf Silanen mit hydrophoben und/oder oleophoben Gruppierungen beruhen, erhöht ist, weil man bisher angenommen hat, daß größere Kettenlängen bei den hydrophoben, und/oder oleophoben Gruppierungen eher zu einer Verringerung der Abriebfestigkeit fuhrt. Es ist dabei bevorzugt, wenn die Kettenlänge der wenigstens einen in dem entsprechenden Silan enthaltenen Alkyl- und/oder Polyfluoralkyl- und/oder Perfluoralkylgruppe zwischen 10 und 30 Kohlenstoffatome beträgt, wobei eine Kettenlänge von 12 bis 20 Kohlenstoffatome aufgrund der Verfügbarkeit der entsprechenden Ausgangsverbindungen sowie der Handhabbarkeit besonders bevorzugt ist.It is particularly surprising for the person skilled in the art that the abrasion resistance of coatings which are produced from the material according to the invention and are based on silanes with hydrophobic and / or oleophobic groups is increased because it has previously been assumed that longer chain lengths are used for the hydrophobic and / or oleophobic groups tend to reduce abrasion resistance. It is preferred if the chain length of the at least one alkyl group contained in the corresponding silane and / or polyfluoroalkyl and / or perfluoroalkyl group is between 10 and 30 carbon atoms, a chain length of 12 to 20 carbon atoms being particularly preferred on account of the availability of the corresponding starting compounds and the ease of handling.
Das erfindungsgemäße Material zur Herstellung abriebfester hydrophober, und/oder oleophober Beschichturigen enthält das vorstehend erwähnte Silan im allgemeinen in einem Lösungsund/oder Emulgationsmittel. Aufgrund von wirtschaftlichen, ökologischen und verfahrenstechnischen Gegebenheiten ist es bevorzugt, wenn dieses Lösungs- und/oder Emulgationsmittel Wasser ist oder zumindest einen hohen Wasseranteil aufweist. Auch wässrige Lösungen von Alkoholen wie Ethanol, Methanol, Propanol, Isopropanol und/oder Butanol (in allen seinen isomeren Formen) sind daher ebenfalls besonders gut als Lösungs- und/oder Emulgationsmittel und somit als Bestandteil des erfindungsgemäßen Materials zur Herstellung abriebfester, hydrophober und/oder oleophober Beschichtungen geeignet.The material according to the invention for producing abrasion-resistant hydrophobic and / or oleophobic coatings generally contains the abovementioned silane in a solvent and / or emulsifier. Due to economic, ecological and procedural conditions, it is preferred if this solvent and / or emulsifying agent is water or at least has a high water content. Aqueous solutions of alcohols such as ethanol, methanol, propanol, isopropanol and / or butanol (in all its isomeric forms) are therefore also particularly good as solvents and / or emulsifiers and thus as a constituent of the material according to the invention for producing abrasion-resistant, hydrophobic and / or oleophobic coatings.
In einer weiteren besonderen Ausführungsforrn der vorliegenden Erfindung enthält das Material zur Herstellung abriebfester, hydrophober und/oder oleophober Beschichtungen weiterhin eine Verbindung, die auf das in dem Material enthaltene und bereits beschriebene Silan, welches insbesondere ein Alkoxysilan ist, als Aktivator wirkt. Es ist dabei bevorzugt, wenn diese Verbindung eine Säure, die durch Protonierung des Sauerstoffs der Alkoxygruppierung die hydrolytische Abspaltung der Alkoxidgruppierung beschleunigt. Als Alkoxidgruppen finden dabei im wesentlichen Methoxygruppen- und Ethoxygruppen Anwendung und die hydrolytische Abspaltung der Alkoxidgruppe ist Ober die Säurestärke der als Aktivator verwendete Säure steuerbar. Es ist dabei besonders bevorzugt, wenn die als Aktivator eingesetzte Säure eine anorganische Säure oder eine organische Säure ist, d.h. insbesondere HC1, H2S04 und H3P04 sowie Essig- oder AmeisensäureIn a further particular embodiment of the present invention, the material for producing abrasion-resistant, hydrophobic and / or oleophobic coatings furthermore contains a compound which acts as an activator on the silane contained in the material and already described, which is in particular an alkoxysilane. It is preferred if this compound is an acid which, by protonating the oxygen of the alkoxy group, accelerates the hydrolytic cleavage of the alkoxide group. Essentially methoxy groups and ethoxy groups are used as alkoxide groups and the hydrolytic cleavage of the alkoxide group can be controlled via the acid strength of the acid used as activator. It is particularly preferred if the acid used as an activator is an inorganic acid or an organic acid, ie in particular HCl, H 2 SO 4 and H 3 PO 4 and acetic or formic acid
Ein weiterer Vorteil des erfindungsgemäßen Materials ist daß sehr breite Anwendungsspektrum. Es können fast sämtliche bekannten natürlichen und synthetischen Substrate mit dem erfindungsgemäßen Material unter Ausbildung von abriebfesten hydrophoben und/oder oleophoben Beschichtungen beschichtet werden. Es ist daher bevorzugt, wenn das Substrat ein glasartiges und/oder keramisches Substrat ist (z.B. Glas, Keramik, Emaille), eine Textilie (z.B. Gardinenstoff, Markiesenstoff, Bekleidungsstoff), eine Faser, Leder, Holz, ein Metall (z.B. Chrom, Messing, Kupfer, Zink, Edelstahl), ein Kunststoff, Papier, Pappe oder ein Naturstoff.Another advantage of the material according to the invention is that it has a very wide range of applications. Almost all known natural and synthetic substrates can be coated with the material according to the invention with the formation of wear-resistant hydrophobic and / or oleophobic coatings. It is therefore preferred if the substrate is a glass-like and / or ceramic substrate (e.g. glass, ceramic, enamel), a textile (e.g. Curtain fabric, awning fabric, clothing fabric), a fiber, leather, wood, a metal (e.g. chrome, brass, copper, zinc, stainless steel), a plastic, paper, cardboard or a natural material.
Bei der Beschichtung des Substrats ist es bevorzugt, wenn die Oberfläche desselben während des Aufbringens der Beschichtung, d.h. während des Aufbringens des erfindungsgemäßen Materials zur Herstellung abreibfester, hydrophober und/oder oleophober Beschichtungen wenigstens Raumtemperatur besitzt. Allgemein liegt die Temperatur für die Durchführung einer derartigen Beschichtung im Bereich von etwa Raumtemperatur bis etwa 400 °C bevorzugt im Bereich von 40 bis 200 °C und besonders bevorzugt im Bereich von 60 bis 170 °C Die bevorzugten Temperaturbereiche für die Durchfuhrung der Beschichtung ergeben sich dabei aus den Temperaturbeständigkeiten der vorzugsweise in dem erfindungsgemäßen Material eingesetzten Silane und/oder der zu beschichtenden Substrate. Weiterhin ist die Höhe der Temperatur bei dem Aufbringen des erfindungsgemäßen Materials für die Schichtbildung von besonderer Bedeutung, da sie die Trocknungsgeschwindigkeit, d.h. die Geschwindigkeit mit der das Lösungsmittel- und/oder Emulsionsmittel entfernt wird, beeinflußt.When coating the substrate, it is preferred if the surface of the same is applied during the application of the coating, i.e. has at least room temperature during the application of the material according to the invention for producing abrasion-resistant, hydrophobic and / or oleophobic coatings. In general, the temperature for carrying out such a coating is in the range from about room temperature to about 400 ° C., preferably in the range from 40 to 200 ° C. and particularly preferably in the range from 60 to 170 ° C. The preferred temperature ranges for the application of the coating result the temperature resistance of the silanes preferably used in the material according to the invention and / or the substrates to be coated. Furthermore, the level of the temperature when applying the material according to the invention is of particular importance for the layer formation, since it determines the drying rate, i.e. affects the rate at which the solvent and / or emulsifier is removed.
Das erfindungsgemäße Material kann weiterhin durch ein beliebiges, dem Fachmann geläufiges Beschichtungsverfahren auf das Substrat aufgebracht werden, wobei es bevorzugt durch Schütten, Fluten, Tauchen oder Schleudern erfolgt und besonders bevorzugt durch Sprühen.The material according to the invention can furthermore be applied to the substrate by any coating method known to the person skilled in the art, it preferably being carried out by pouring, flooding, dipping or spinning and particularly preferably by spraying.
In einer besonderen Ausgestaltung ist es vorteilhaft, wenn nach dem Aufbringen des erfindungsgemäßen Materials ein sogenanntes Nachtempern erfolgt. Bei diesem Nachtempern wird dem Substrat weiterhin Wärme zugeführt, vorteilhafterweise so, daß die Substrattemperatur gehalten wird. Hierdurch ist nicht nur eine Trocknung möglich, sondern je nach den gewählten Bedingungen und den eingesetzten Silanen auch eine Vernetzung der Moleküle innerhalb der Beschichtung.In a special embodiment, it is advantageous if after the application of the material according to the invention so-called post-annealing takes place. In this post-annealing, heat is further supplied to the substrate, advantageously in such a way that the substrate temperature is maintained. This not only enables drying, but also cross-linking of the molecules within the coating, depending on the selected conditions and the silanes used.
Die vorliegende Erfindung wird nachfolgend anhand von Beispielen näher erläutert, wobei diese keinesfalls zur Beschränkung der Erfindung auszulegen sind.The present invention is explained in more detail below with the aid of examples, which are in no way to be interpreted as restricting the invention.
Die Herstellung der zum Einsatz im erfindungsgemäßen Material vorgesehenen Silane, insbesondere Trialkoxysilane, sind dem Fachmann grundsätzlich geläufig, so daß eine Beschreibung des Herstellungsverfahrens an dieser Stelle unterbleiben kann. Die Beschichtung von z.B. einer Sanitärkeramik erfolgt im allgemeinen wie folgt.The preparation of the silanes intended for use in the material according to the invention, in particular trialkoxysilanes, is generally familiar to the person skilled in the art, so that a Description of the manufacturing process can be omitted here. The coating of, for example, a sanitary ware is generally carried out as follows.
Beispiel 1example 1
20 g lH,lH,2H,2H-Perfluorododecyltriethoxysilan werden mit 200 g Ethanol und 4 g 10 %-iger Schwefelsäure versetzt und anschließend 15 Minuten intensiv bei Raumtemperatur gerührt. Die Lösung wird auf Glas sprühbeschichtet und anschließend 1 Std. bei 200 °C getrocknet.20 g of 1H, 1H, 2H, 2H-perfluorododecyltriethoxysilane are mixed with 200 g of ethanol and 4 g of 10% sulfuric acid and then stirred intensively for 15 minutes at room temperature. The solution is spray coated on glass and then dried at 200 ° C. for 1 hour.
Beispiel 2Example 2
20 g eines Dodecyltriethoxysilan werden mit 200 g Ethanol und 4 g 10 %-iger Schwefelsäure versetzt und anschließend, 15 Minuten intensiv bei Raumtemperatur gerührt. Die Lösung wird auf Glas sprühbeschichtet und anschließend 1 Std. bei 200 °C getrocknet,20 g of a dodecyltriethoxysilane are mixed with 200 g of ethanol and 4 g of 10% sulfuric acid and then stirred intensively for 15 minutes at room temperature. The solution is spray-coated on glass and then dried at 200 ° C. for 1 hour.
Beispiel 3Example 3
Wie Beispiel 2, jedoch wird statt des Ethanols ein Gemisch aus 200 g Wasser und 1 g Byk348 (Byk-Chemie eingesetzt).Like example 2, but instead of ethanol a mixture of 200 g water and 1 g Byk348 (Byk-Chemie) is used.
Beispiel 4Example 4
Wie Beispiel 2, jedoch wird statt des Ethanols ein Gemisch aus 200 g Wasser und 1 g Byk348 (Byk-Chemie) eingesetzt.Like example 2, but instead of the ethanol a mixture of 200 g water and 1 g Byk348 (Byk-Chemie) is used.
Zum Nachweis der verbesserten Abriebbeständigkeit der mit dem erfindungsgemäßen Material hergestellten Beschichtungen im Vergleich zu Materialien aus dem Stand der Technik wurden Vergleichsversuche durchgeführt. Dabei wurden die Beschichtungsmaterialien jeweils wie in dem vorangehenden Beispielen auf eine Sanitärkeramik aufgesprüht und 1 Std. bei 250 °C getrocknet. Die Versuchsbedingungen sind in der nachfolgenden Tabelle angegeben. Tabelle 1Comparative tests were carried out to demonstrate the improved abrasion resistance of the coatings produced with the material according to the invention compared to materials from the prior art. The coating materials were each sprayed onto a sanitary ceramic as in the preceding examples and dried at 250 ° C. for 1 hour. The test conditions are given in the table below. Table 1
Vergleich der Abriebbeständigkeiten unterschiedlicher hydrophober und/oder oleophober BeschichtungenComparison of the abrasion resistance of different hydrophobic and / or oleophobic coatings
Figure imgf000007_0001
Figure imgf000007_0001

Claims

Patentansprüche claims
1. Material zur Herstellung abriebfester, hydrophober und/oder oleophober Beschichtungen, dadurch gekennzeichnet, daß das Material ein Alkoxysilan bzw. dessen Hydrolysat mit wenigstens einer Alkyl- und/oder Polyfiuoralkyl- und/oder Perfluoralkylgruppe oder eine Mischung der vorgenannten Silane bzw. Silanhydrolysate mit einer Kettenlänge von mindestens 10 Kohlenstoffatomen enthält.1. Material for the production of abrasion-resistant, hydrophobic and / or oleophobic coatings, characterized in that the material contains an alkoxysilane or its hydrolyzate with at least one alkyl and / or polyfluoroalkyl and / or perfluoroalkyl group or a mixture of the aforementioned silanes or silane hydrolyzates contains a chain length of at least 10 carbon atoms.
2. Material gemäß Anspruch 1, dadurch gekennzeichnet, daß das Material weiterhin eine als Aktivator auf das Alkoxysilan wirkende Verbindung enthält.2. Material according to claim 1, characterized in that the material further contains a compound acting as an activator on the alkoxysilane.
3. Material gemäß Anspruch 2, dadurch gekennzeichnet, daß die als Aktivator wirkende Verbindung eine Säure ist, insbesondere eine anorganische Säure oder eine organische Säure, ausgewählt aus Salzsäure, Schwefelsäure, Phosphorsäure, Essigsäure oder Ameisensäure.3. Material according to claim 2, characterized in that the compound acting as an activator is an acid, in particular an inorganic acid or an organic acid selected from hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid or formic acid.
4. Material gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Kettenlänge der wenigstens einen Alkyl- und/oder Polyfiuoralkyl- und/oder Perfluoralkylgruppe zwischen 10 und 30 Kohlenstoffatome beträgt, insbesondere 12 bis 20 Kohlenstoffatome.4. Material according to any one of the preceding claims, characterized in that the chain length of the at least one alkyl and / or polyfluoroalkyl and / or perfluoroalkyl group is between 10 and 30 carbon atoms, in particular 12 to 20 carbon atoms.
5. Material gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß es weiterhin Wasser als Lösungs- und/oder Emulgationsmittel enthält.5. Material according to any one of the preceding claims, characterized in that it further contains water as a solvent and / or emulsifying agent.
6. Verwendung des Materials gemäß einem der vorhergehenden Ansprüche zur Beschichtung eines Substrats, dadurch gekennzeichnet, daß das Substrat ein glasartiges oder keramisches Substrat, eine Textilie, eine Faser, Leder, Holz, ein Metall, Kunststoff, Papier, Pappe oder ein Naturstoff ist.6. Use of the material according to one of the preceding claims for coating a substrate, characterized in that the substrate is a glass-like or ceramic substrate, a textile, a fiber, leather, wood, a metal, plastic, paper, cardboard or a natural material.
7. Verfahren gemäß Anspruch 6, dadurch gekennzeichnet, daß die Oberfläche des Substrats während des Aufbringens der Beschichtung wenigstens Raumtemperatur besitzt. 7. The method according to claim 6, characterized in that the surface of the substrate has at least room temperature during the application of the coating.
8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, daß die Oberfläche des Substrats eine Temperatur im Bereich von Raumtemperatur bis 400 °C besitzt, insbesondere eine Temperatur im Bereich von 40 bis 200 °C besonders bevorzugt von 60 bis 170 °C.8. The method according to claim 7, characterized in that the surface of the substrate has a temperature in the range from room temperature to 400 ° C, in particular a temperature in the range from 40 to 200 ° C, particularly preferably from 60 to 170 ° C.
9. Verfahren gemäß einem der Ansprüche 6 bis 8, dadurch gekennzeichnet, daß das Aufbringen des Materials durch Schütten, Fluten, Tauchen, Walzen oder Schleudern und insbesondere durch Sprühen erfolgt.9. The method according to any one of claims 6 to 8, characterized in that the application of the material is carried out by pouring, flooding, dipping, rolling or spinning and in particular by spraying.
10. Verfahren gemäß einem der Ansprüche 6 bis 9, dadurch gekennzeichnet, daß nach dem Aufbringen des Materials ein Nachtempern erfolgt, wobei das Nachtempern insbesondere bei einer Temperatu r erfolgt, die der Temperatur des Substrats während des Aufbringens des Materials entspricht. 10. The method according to any one of claims 6 to 9, characterized in that after the application of the material an after-annealing takes place, the after-annealing taking place in particular at a temperature r which corresponds to the temperature of the substrate during the application of the material.
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