WO2003082998A1 - Water-based coating fluid - Google Patents

Water-based coating fluid Download PDF

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Publication number
WO2003082998A1
WO2003082998A1 PCT/DE2003/001028 DE0301028W WO03082998A1 WO 2003082998 A1 WO2003082998 A1 WO 2003082998A1 DE 0301028 W DE0301028 W DE 0301028W WO 03082998 A1 WO03082998 A1 WO 03082998A1
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WIPO (PCT)
Prior art keywords
water
silane
coating
hydrolysis
coating fluid
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PCT/DE2003/001028
Other languages
German (de)
French (fr)
Inventor
Rüdiger Nass
Gerhard Jonschker
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Nanogate Technologies Gmbh
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Publication date
Application filed by Nanogate Technologies Gmbh filed Critical Nanogate Technologies Gmbh
Priority to AU2003229500A priority Critical patent/AU2003229500A1/en
Priority to DE10391116T priority patent/DE10391116D2/en
Publication of WO2003082998A1 publication Critical patent/WO2003082998A1/en

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Classifications

    • 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
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/62—Coating or impregnation with organic materials
    • C04B41/64—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
    • 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

Definitions

  • the present invention relates to what is claimed in the preamble.
  • the present invention is concerned with water-based coatings which harden at room temperature.
  • Coatings and coating materials based on water, also with non-stick properties, are known per se, like their production.
  • the actual effective anti-adhesive coating component is thus made water-compatible by auxiliaries, some of which remain in the product and / or impede self-crosslinking or crosslinking with the substrate and / or have to be removed in a complex, in particular thermal manner, so that at all the desired typically hydrophobic effect is obtained.
  • the object of the present invention is to provide something new for commercial use.
  • the invention thus proposes a method for producing a coating fluid, in which a hydrophobic and / or oleophobic silane with a water-miscible solution medium added, water added for pre-hydrolysis and the pre-hydrolyzate is diluted.
  • auxiliaries it was found that it is not necessary to use auxiliaries in order to obtain coating solutions which can be used according to the invention for days and weeks. It was found that the absence of hydrophilic auxiliaries significantly increases the performance of the coating material and that the coatings obtained are characterized by rapid curing at room temperature and a previously unattained durability.
  • the hydrophobic silanes can form a surfactant structure upon hydrolysis by forming Si-OH groups in conjunction with the hydrophobic / oleophobic residue and can self-disperse in water. This structure can only act as a surfactant until condensates are formed by Si-O-Si bonding and the hydrophobic properties of the condensate dominate. If the hydrolyzed silane is dispersed in water, there is a high probability that a micellar structure will result, in which the Si-OH groups are present "outwards" to the water side and the hydrophobic / oleophobic residues protrude inside the micelle.
  • the Si-OH group-rich coating materials are enriched by the evaporation of the water during application and then quickly condense with themselves and the substrate. This enables very firmly adhering coatings to be produced.
  • certain admixtures and auxiliary substances can be added to the fluid to improve the application and coating properties, which improve the properties and do not impair them. It is thus possible to add nanoparticles such as Ti02, Si02, Zr02, Sn02, ' Zn02, exfoliated layered silicates (all types known to the person skilled in the art); Surfactants can be added in a formulation as cleaning agents with a coating effect, as spreading aids, etc., with the addition of fluorosurfactants being preferred. Metal alkoxides of Zr, Ti, Sn, Zn, Al and others can be added as well as other salts in order to obtain known associated properties. Defoamers, odorants, dyes and pigments and / or to further improve the properties and / or achieve other properties, fluoropolymers can also be added in dissolved or dispersed form.
  • nanoparticles such as Ti02, Si02, Zr02, Sn02, ' Zn02, exfoliated layered silicates (all types
  • silanes can be used as silanes per se, in particular also hydrophilic silanes in low concentrations ⁇ 20% based on the solid.
  • the silanes actually used depend on the behavior actually desired. If a primarily water-repellent behavior is desired, alkyl silanes can be used; on the other hand, if water and oil repellent properties are desired, pure fluoroalkyl silanes or mixtures containing fluroalkyl silanes can be used.
  • Curing is preferably carried out at room temperature; In order to accelerate the curing processes and / or to be able to use crosslinking compounds only at elevated temperatures, it is also possible to effect curing at up to 350 ° C. For this purpose, it is possible, for example in a manufacturing process for tiles or other ceramics, to utilize the residual heat of production by applying the fluid to the heated surface or the fluid to be cold
  • the field of application includes a large number of applications, such as textiles, in which the coating material is introduced as a concentrate in the last rinse, the fluid is applied to textiles before ironing or drying, in particular sprayed on, leather, metal, wood, plastics, but also and in particular mineral surfaces such as concrete, natural stones such as sandstone, granite or marble, glasses, in particular mineral glasses, in particular flat glass such as window panes and / or ceramic materials, in particular sanitary ceramics, in particular tiles, the use of the coating fluid here having the advantage that it due to the fact that less than 5% organic solvents such as alcohols etc. are contained in the finished coating fluid when sprayed into a manufacturing oven without Explosion protection can be done.
  • a cleaning care coating for household purposes is possible.
  • Example 1 2.56 g of tridecafluorooctyltriethoxysilane is dissolved in 26.2 g of isopropanol and mixed with 0.06 g of perfluorooctanoic acid and 11.3 g of deionized water. The mixture is stirred at room temperature for 30 minutes and then poured into 460 g of deionized water. After stirring for 5 minutes, the water-based coating solution is sprayed with a pump trigger onto a window pane which has been thoroughly pre-cleaned with an abrasive cleaner and water. The coating solution forms a uniform film with foam bubbles, but it wets homogeneously.
  • the finished coating solution can be used for coating for several weeks if the solution is stored at ⁇ 20 ° C.
  • Example 2 The solution from Example 1 is sprayed on concrete block. After drying, you keep a very well hydrophobic and oleophobic surface.
  • Example 3 The solution from Example 1 is mixed with 0.5 g of lauryl sulfate and stirred for 30 minutes.
  • Example 4 The solution from Example 1 is sprayed onto a variety of surfaces to be coated using a commercially available spray gun (e.g. Sata Jet) such that a thin, closed film is formed in each case.
  • a commercially available spray gun e.g. Sata Jet
  • the amount required has been shown to depend on the surface properties of the substrate (smooth or rough, absorbent or non-absorbent) and is approx. 10-20 g / sqm. After drying, a largely transparent and invisible film of silane condensate is distinguished.
  • the coated tiles and glass plates were rubbed in a defined manner using an abrasion tester from Braive Instruments "Washability Tester" and then the contact angle against water was measured.
  • a high contact angle indicates an intact coating
  • a low contact angle indicates a layer damaged by abrasion.
  • a 4 x 9 cm mason sponge soaked with scouring milk was used as the abrasion medium, the coating weight was 500 g and the plates were cleaned with water and isopropanol after the abrasion test before determining the contact angle.
  • the error of the measurement taking into account all sources of error was approx. 4%. From the observation of the prior art for solvent-based coatings, it can be concluded that a contact angle of> 80 ° after 1000 cycles can be assessed as very good.
  • Example 5 The solution from Example 1 is injected into a circulating air drying cabinet with a capacity of approximately 60 liters by means of a spray gun. The temperature of the drying cabinet during injection is 250 ° C. The objects to be coated (glazed tiles and glass plates) are distributed in the cabinet at various heights and arrangements.
  • the drying cabinet is kept at 250 ° C. for a further 30 minutes, then switched off. After cooling, the test specimens to be coated are examined for abrasion resistance using the method described in Example 4.
  • the result shows the excellent abrasion resistance of the coatings applied by this process.

Abstract

The invention relates to a method for producing a coating fluid. Said method is characterised in that a water-miscible solvent is added to a hydrophobic and/or oleophobic silane, water is added for the prehydrolysis of the mixture and the prehydrolysate is diluted.

Description

Titel: Beschichtungsfluid auf WasserbasisTitle: Water-based coating fluid
Beschreibungdescription
Die vorliegende Erfindung betrifft das oberbegrifflich Beanspruchte. Damit befaßt sich die vorliegende Erfindung mit wasserbasierenden und bei Raumtemperatur erhärtenden Be- Schichtungen.The present invention relates to what is claimed in the preamble. The present invention is concerned with water-based coatings which harden at room temperature.
Beschichtungen und Beschichtungsmaterialien auf Wasserbasis auch mit Antihafteigenschaften sind, wie deren Herstellung, per se bekannt.Coatings and coating materials based on water, also with non-stick properties, are known per se, like their production.
So wurde die Herstellung von Beschichtungsmaterialien beschrieben, die aus Chlorsilanen mit teilfluorierten Resten durch Veresterung eines Siliziumatoms mit hydrophilen Gruppen (Etheralkohole) bestehen, wobei die hydrophilen Gruppen Was- serkompatibilität vermitteln sollen. Problematisch ist, daß diese hydrophilen Gruppen abzuspalten sind, damit das Be- schichtungs aterial vernetzen oder eine Verbindung mit dem Untergrund eingehen kann.The production of coating materials which consist of chlorosilanes with partially fluorinated residues by esterification of a silicon atom with hydrophilic groups (ether alcohols) has been described, the hydrophilic groups being intended to impart water compatibility. The problem is that these hydrophilic groups have to be split off so that the coating can cross-link material or form a connection with the substrate.
Weiter ist bekannt, Beschichtungsmaterialien durch Kokonden- sation von hydrophilen mit hydrophoben Silanen herzustellen. Nachteilig ist, daß hydrophile Gruppen im Beschichtungsmate- rial verbleiben, was die Qualität der resultierenden Beschichtungen negativ beeinflußt.It is also known to produce coating materials by cocondensing hydrophilic with hydrophobic silanes. It is disadvantageous that hydrophilic groups remain in the coating material, which has a negative effect on the quality of the resulting coatings.
Bekannt ist auch, wasserbasierende Beschichtungsmaterialien durch Bildung von salzartigen Strukturen mit teilfluorierten Silanen herzustellen. Hier sind die verwendeten Hilfsstoffe quartäre Ammoniumsalze, die entfernbar sind. Dazu ist allerdings das Einbrennen bei Temperaturen oberhalb von 200 ° Celsius erforderlich, um dann eine Vernetzung mit dem Untergrund und innerhalb der Beschichtung zu ermöglichen.It is also known to use water-based coating materials by forming salt-like structures with partially fluorinated ones To produce silanes. The auxiliaries used here are quaternary ammonium salts which can be removed. However, this requires baking at temperatures above 200 ° Celsius in order to enable cross-linking with the substrate and within the coating.
Im Stand der Technik wird somit die eigentliche wirksame An- tihaftbeschichtungskomponente durch Hilfsstoffe wasserkompatibel gemacht, die teilweise im Produkt bleiben und/oder die Selbstvernetzung bzw. die Vernetzung mit dem Untergrund behindern und/oder auf aufwändige, insbesondere thermische Weise entfernt werden müssen, damit überhaupt der gewünschte typisch hydrophobe Effekt erhalten wird.In the prior art, the actual effective anti-adhesive coating component is thus made water-compatible by auxiliaries, some of which remain in the product and / or impede self-crosslinking or crosslinking with the substrate and / or have to be removed in a complex, in particular thermal manner, so that at all the desired typically hydrophobic effect is obtained.
Wünschenswert ist daher, ein Beschichtungsmaterial zu erhalten, das wasserbasiert ist, aber dennoch praktisch rein hydrophobe und/oder oleophobe Wirkkomponenten aufweist, wenigstens aber in seiner Leistungsfähigkeit nicht durch die Verwendung hydrophiler Hilfsstoffe signifikant beeinträchtigt ist.It is therefore desirable to obtain a coating material which is water-based but nevertheless has practically purely hydrophobic and / or oleophobic active components, but at least its performance is not significantly impaired by the use of hydrophilic auxiliaries.
Die Aufgabe der vorliegenden Erfindung besteht darin, Neues für die gewerbliche Anwendung bereitzustellen.The object of the present invention is to provide something new for commercial use.
Die Lösung dieser Aufgabe wird in unabhängiger Form beansprucht. Bevorzugte Ausführungsformen finden sich in den Unteransprüchen.The solution to this problem is claimed in an independent form. Preferred embodiments can be found in the subclaims.
Damit schlägt die Erfindung ein Verfahren zur Herstellung ei- nes Beschichtungsfluids vor, bei welchem ein hydrophobes und/oder oleophobes Silan mit einem wassermischbaren Lösungs- mittel versetzt, Wasser zur Vorhydrolyse zugegeben und das Vorhydrolysat verdünnt wird.The invention thus proposes a method for producing a coating fluid, in which a hydrophobic and / or oleophobic silane with a water-miscible solution medium added, water added for pre-hydrolysis and the pre-hydrolyzate is diluted.
Es wurde überraschend festgestellt, daß es möglich ist, eine über Wochen stabile Dispersion von hochgradig hydropho- bem/oleophobem Silan in Wasser dadurch herzustellen, daß die Silane in einem ersten Schritt in einem geeigneten Lösungsmittel aufgenommen und danach mit Wasser vorhydrolysiert werden, bevor sie in Wasser mit geeignetem pH-Wert, nämlich leicht angesäuert, dispergiert werden.It was surprisingly found that it is possible to produce a highly stable hydrophobic / oleophobic silane dispersion in water for weeks by taking up the silanes in a suitable solvent in a first step and then pre-hydrolyzing them with water before they are dissolved in water Water with a suitable pH, namely slightly acidified, can be dispersed.
Es wurde dabei gefunden, daß es nicht erforderlich ist, Hilfsstoffe zu verwenden, um über Tage und Wochen erfindungsgemäß anwendbare Beschichtungslösungen zu erhalten. Es wurde festgestellt, daß die Abwesenheit hydrophiler Hilfsstoffe die Leistungsfähigkeit des Beschichtungsmaterials wesentlich steigert und sich die erhaltenen Beschichtungen durch eine rasche Aushärtung bei Raumtemperatur und eine zuvor noch nicht erreichte Dauerhaftigkeit auszeichnen.It was found that it is not necessary to use auxiliaries in order to obtain coating solutions which can be used according to the invention for days and weeks. It was found that the absence of hydrophilic auxiliaries significantly increases the performance of the coating material and that the coatings obtained are characterized by rapid curing at room temperature and a previously unattained durability.
Die der Erfindung zugrundeliegenden chemischen Mechanismen sind noch nicht vollständig verstanden. Es wird angenommen, daß eine Erklärung darin liegen könnte, daß die hydrophoben Silane bei der Hydrolyse durch Ausbildung von Si-OH-Gruppen in Verbindung mit dem hydrophoben/oleophoben Rest eine Ten- sidstruktur ausbilden und sich selbst in Wasser dispergieren können. Diese Struktur kann nur so lange tensidisch wirken, bis Kondensate durch Si-O-Si-Bindung entstanden sind und die hydrophoben Eigenschaften des Kondensats dominieren. Ist das hydrolysierte Silan in Wasser dispergiert, dann stellt sich mit hoher Wahrscheinlichkeit eine micellare Struktur ein, bei der die Si-OH-Gruppen nach „außen" zur Wasserseite vorliegen und die hydrophoben/oleophoben Reste ins Innere der Micelle ragen. Bei ausreichend niedrigen Feststoffgehalten ist die Wahrscheinlichkeit einer Kondensation der Si-OH-Gruppen so reduziert, daß eine hohe Haltbarkeit der Beschichtungslösung resultiert. Die Si-OH-Gruppen-reichen Beschichtungsmaterialien werden bei der Applikation durch das Verdampfen des Wassers angereichert und kondensieren dann rasch mit sich und dem Untergrund. Dadurch können sehr fest haftende Überzüge hergestellt werden.The chemical mechanisms on which the invention is based are not yet fully understood. It is believed that one explanation could be that the hydrophobic silanes can form a surfactant structure upon hydrolysis by forming Si-OH groups in conjunction with the hydrophobic / oleophobic residue and can self-disperse in water. This structure can only act as a surfactant until condensates are formed by Si-O-Si bonding and the hydrophobic properties of the condensate dominate. If the hydrolyzed silane is dispersed in water, there is a high probability that a micellar structure will result, in which the Si-OH groups are present "outwards" to the water side and the hydrophobic / oleophobic residues protrude inside the micelle. If the solids content is sufficiently low, the likelihood of condensation of the Si-OH groups is reduced so that the coating solution has a long shelf life. The Si-OH group-rich coating materials are enriched by the evaporation of the water during application and then quickly condense with themselves and the substrate. This enables very firmly adhering coatings to be produced.
Es sei angemerkt, daß dem Fluid zur Verbesserung der Applikations- und Beschichtungseigenschaften bestimmte Beimengungen und Hilfsstoffe zugesetzt werden können, die die Eigenschaften verbessern und nicht verschlechtern. So ist es möglich, Nanoteilchen, wie Ti02, Si02, Zr02, Sn02,' Zn02, exfolierte Schichtsilikate (alle dem Fachmann bekannten Typen) beizufügen; Tenside können in einer Formulierung als Reinigungsmittel mit Beschichtungseffekt, als Spreitungshilfsmittel usw. zugesetzt werden, wobei der Zusatz von Fluortensiden bevor- zugt ist. Metallalkoxide von Zr, Ti, Sn, Zn, AI u. a. können ebenso wie andere Salze zugesetzt werden, um damit bekannte verbundene Eigenschaften zu erhalten. Weiter sind Entschäumer, Geruchsstoffe, Farbstoffe und Pigmente und/oder zur weiteren Verbesserung der Eigenschaften und/oder Erzielen ande- rer Eigenschaften Fluorpolymere in gelöster oder dispergier- ter Form zusetzbar.It should be noted that certain admixtures and auxiliary substances can be added to the fluid to improve the application and coating properties, which improve the properties and do not impair them. It is thus possible to add nanoparticles such as Ti02, Si02, Zr02, Sn02, ' Zn02, exfoliated layered silicates (all types known to the person skilled in the art); Surfactants can be added in a formulation as cleaning agents with a coating effect, as spreading aids, etc., with the addition of fluorosurfactants being preferred. Metal alkoxides of Zr, Ti, Sn, Zn, Al and others can be added as well as other salts in order to obtain known associated properties. Defoamers, odorants, dyes and pigments and / or to further improve the properties and / or achieve other properties, fluoropolymers can also be added in dissolved or dispersed form.
Es sei darauf hingewiesen, daß als Silane per se alle bekannten Silane herangezogen werden können, insbesondere auch hy- drophile Silane in geringen Konzentrationen < 20 % bezogen auf den Feststoff. Bevorzugt sind allerdings teilfluorierte Alkyl-/Aryl-Silane, insbesondere Tridecafluoroctyltriethoxy- silan. Die tatsächlich verwendeten Silane sind abhängig von dem tatsächlich gewünschten Verhalten. Wird ein primär wasserabweisendes Verhalten gewünscht, können Alkyl-Silane verwendet werden, werden hingegen wasser- und ölabweisende Ei- genschaften gewünscht, so können reine Fluoralkyl-Silane oder Fluroalkyl-Silane enthaltende Gemsiche verwendet werden.It should be pointed out that all known silanes can be used as silanes per se, in particular also hydrophilic silanes in low concentrations <20% based on the solid. However, preference is given to partially fluorinated alkyl / aryl silanes, in particular tridecafluorooctyltriethoxy silane. The silanes actually used depend on the behavior actually desired. If a primarily water-repellent behavior is desired, alkyl silanes can be used; on the other hand, if water and oil repellent properties are desired, pure fluoroalkyl silanes or mixtures containing fluroalkyl silanes can be used.
Bevorzugt erfolgt die Aushärtung bei Raumtemperatur; um die Aushärtungsprozesse zu beschleunigen und/oder erst bei erhöh- ten Temperaturen vernetzende Verbindungen einsetzen zu können, ist es auch möglich, eine Aushärtung bei bis zu 350° C zu bewirken. Dazu ist es möglich, etwa in einem Herstellungsprozeß für Fliesen oder andere Keramik, die Restwärme der Produktion auszunutzen, indem das Fluid auf die erwärmte Oberfläche aufgebracht wird oder das Fluid wird auf kalteCuring is preferably carried out at room temperature; In order to accelerate the curing processes and / or to be able to use crosslinking compounds only at elevated temperatures, it is also possible to effect curing at up to 350 ° C. For this purpose, it is possible, for example in a manufacturing process for tiles or other ceramics, to utilize the residual heat of production by applying the fluid to the heated surface or the fluid to be cold
Oberflächen aufgebracht und anschließend zumindest in der Gegenstandsmitte oberflächlich erwärmt.Surfaces applied and then superficially heated at least in the middle of the object.
Der Anwendungsbereich umfaßt eine Vielzahl von Anwendungen, wie Textilien, bei welchen das Beschichtungsmaterial im letzen Spülgang als Konzentrat eingefüllt wird, das Fluid auf Textilien vor dem Bügeln oder Trocknen aufgebracht, insbesondere aufgesprüht wird, Leder, Metall, Holz, Kunststoffe, aber auch und insbesondere mineralische Oberflächen wie Beton, na- türliche Steine wie Sandstein, Granit oder Marmor, Gläser, insbesondere mineralische Gläser, insbesondere Flachglas wie Fensterscheiben und/oder keramische Materialien, insbesondere Sanitärkeramiken, insbesondere Fliesen, wobei die Verwendung des Beschichtungsfluids hier den Vorteil besitzt, daß es auf Grund des Umstandes, daß weniger als 5 % organische Lösungsmittel wie Alkohole usw. in dem fertigen Beschichtungsfluid enthalten sind, beim Einsprühen in einen Fertigungsofen ohne Explosionsschutz erfolgen kann. Eine reinigende Pflegebe- schichtung zu Haushaltszwecken ist möglich.The field of application includes a large number of applications, such as textiles, in which the coating material is introduced as a concentrate in the last rinse, the fluid is applied to textiles before ironing or drying, in particular sprayed on, leather, metal, wood, plastics, but also and in particular mineral surfaces such as concrete, natural stones such as sandstone, granite or marble, glasses, in particular mineral glasses, in particular flat glass such as window panes and / or ceramic materials, in particular sanitary ceramics, in particular tiles, the use of the coating fluid here having the advantage that it due to the fact that less than 5% organic solvents such as alcohols etc. are contained in the finished coating fluid when sprayed into a manufacturing oven without Explosion protection can be done. A cleaning care coating for household purposes is possible.
Die Erfindung wird im folgenden uns beispielsweise anhand der Beispiele ohne Bezugnahme auf eine Zeichnung beschrieben:The invention is described below, for example, using the examples without reference to a drawing:
Beispiel 1: 2,56 g Tridecafluoroctyltriethoxysilan wird in 26,2 g Isopropanol gelöst und mit 0,06 g Perfluoroctansäure und 11,3 g deionisiertem Wasser gemischt. Die Mischung wird 30 Minuten bei Raumtemperatur gerührt und dann in 460 g deionisiertes Wasser gegossen. Nach 5 Minuten Rühren wird die wasserbasierende Beschich- tungslösung mit einem Pumptrigger auf eine Fensterscheibe gesprüht, die vorher mit einem abrasiven Reiniger und Wasser gründlich vorgereinigt wurde. Die Beschichtungslösung bildet einen gleichmäßigen Film mit Schaumbläschen, der aber homogen benetzt.Example 1: 2.56 g of tridecafluorooctyltriethoxysilane is dissolved in 26.2 g of isopropanol and mixed with 0.06 g of perfluorooctanoic acid and 11.3 g of deionized water. The mixture is stirred at room temperature for 30 minutes and then poured into 460 g of deionized water. After stirring for 5 minutes, the water-based coating solution is sprayed with a pump trigger onto a window pane which has been thoroughly pre-cleaned with an abrasive cleaner and water. The coating solution forms a uniform film with foam bubbles, but it wets homogeneously.
Nach dem Ablüften der Oberfläche bildet sich eine wasser- und ölabweisende Beschichtung aus, die nach 60 Minuten Aushärtezeit eine sehr gute Abriebfestigkeit aufweist.After the surface has been vented, a water- and oil-repellent coating is formed, which has a very good abrasion resistance after 60 minutes of curing.
Die fertige Beschichtungslösung kann mehrere Wochen zur Beschichtung eingesetzt werden, wenn die Lösung bei < 20° C gelagert wird.The finished coating solution can be used for coating for several weeks if the solution is stored at <20 ° C.
Beispiel 2: Die Lösung aus Beispiel 1 wird auf Betonstein satt aufgesprüht. Nach dem Durchtrocknen er- hält man eine sehr gut hydrophobierte und oleophobierte Oberfläche.Example 2: The solution from Example 1 is sprayed on concrete block. After drying, you keep a very well hydrophobic and oleophobic surface.
Beispiel 3: Die Lösung aus Beispiel 1 wird mit 0,5 g Lau- rylsulfat versetzt und 30 Minuten gerührt.Example 3: The solution from Example 1 is mixed with 0.5 g of lauryl sulfate and stirred for 30 minutes.
Mit dieser Lösung wird eine haushaltsüblich verschmutzte Fensterglasscheibe unter Zuhilfenahme von Einweg-Haushaltstüchern gereinigt. Nach dem Abtrocknen zeigt sich, daß die Oberfläche ebenfalls mit einer wasser- und ölabweisenden Beschichtung ausgerüstet wurde. Die Dauerhaftigkeit der Beschichtung betrug ca. 50 % der von Beispiel 1.With this solution, a window glass pane that is normally dirty in the household is cleaned with the help of disposable household towels. After drying it is evident that the surface has also been treated with a water and oil repellent coating. The durability of the coating was approximately 50% of that of Example 1.
Beispiel 4: Die Lösung aus Beispiel 1 wird mit einer handelsüblichen Lackierpistole (z.B. Sata Jet) so auf verschiedene, zu beschichtende Oberflächen gesprüht, dass sich jeweils ein dünner geschlossener Film ausbildet. Die benötigte Men- ge erwies sich also von der Oberflächenbeschaffenheit des Substrates (glatt oder rau, saugend oder nicht saugend) abhängig und beträgt ca. 10-20 g/qm. Nach dem Trocknen zeichnet sich ein weitgehend transparenter und nicht sichtbarer Film aus Silan-Kondensat aus.Example 4: The solution from Example 1 is sprayed onto a variety of surfaces to be coated using a commercially available spray gun (e.g. Sata Jet) such that a thin, closed film is formed in each case. The amount required has been shown to depend on the surface properties of the substrate (smooth or rough, absorbent or non-absorbent) and is approx. 10-20 g / sqm. After drying, a largely transparent and invisible film of silane condensate is distinguished.
Eventuell durch Überschussmaterial oder Schau bildung auftretende Schlieren konnten mit einem trockenen Baumwolltuch leicht entfernt werden.Any streaks that may appear due to excess material or show formation could be easily removed with a dry cotton cloth.
Zum Vergleich wurden handelsübliche, glasierte Fliesen und Glasplatten nach verschiedenen Verfahren behandelt und anschließend die Beschichtung auf ihre Leistungsfähigkeit untersucht.For comparison, commercial, glazed tiles and glass plates were made according to different Treated procedures and then examined the performance of the coating.
Figure imgf000009_0001
Figure imgf000009_0001
Zur Beurteilung der Leistungsfähigkeit wurden die beschichteten Fliesen und Glasplatten mit einem Abriebsprüfgerät der Fa. Braive Instruments „Washabilitytester" definiert abgerieben und anschließend der Kontaktwinkel gegen Wasser gemessen. Dabei zeigt ein hoher Kontaktwinkel eine intakte Beschichtung, ein niedriger Kontaktwinkel eine durch Abrieb beschädigte Schicht an. Als Abriebmedim wurde ein mit Scheuermilch getränkter Maurerschwamm der Abmessung 4 x 9 cm benutzt. Das Auflagegewicht betrug 500 g. Die Platten wurden nach dem Abriebtest vor der Bestimmung des Kontaktwinkels mit Wasser und Isopropanol gereinigt. Der Fehler der Messung unter Berücksichtigung aller Fehlerquellen betrug ca. 4 %. Aus der Beobachtung des Standes der Technik bei lösungsmittelbasierten Beschichtungen kann geschlossen werden, dass ein Kontaktwinkel von > 80 ° nach 1000 Zyklen als sehr gut beurteilt werden kann.To assess the performance, the coated tiles and glass plates were rubbed in a defined manner using an abrasion tester from Braive Instruments "Washability Tester" and then the contact angle against water was measured. A high contact angle indicates an intact coating, a low contact angle indicates a layer damaged by abrasion. A 4 x 9 cm mason sponge soaked with scouring milk was used as the abrasion medium, the coating weight was 500 g and the plates were cleaned with water and isopropanol after the abrasion test before determining the contact angle. The error of the measurement taking into account all sources of error was approx. 4%. From the observation of the prior art for solvent-based coatings, it can be concluded that a contact angle of> 80 ° after 1000 cycles can be assessed as very good.
Figure imgf000010_0001
Figure imgf000010_0001
Die Messwerte zeigen die hervorragende Abriebsstabilität der nach diesem Verfahren aufgebrachten Antihaftbeschichtungen. Beispiel 5 Die Lösung aus Beispiel 1 wird in einen Um- lufttrockenschrank mit ca. 60 1 Fassungsvermögen durch eine Spritzpistole eingedüst. Die Temperatur des Trockenschranks beträgt bei der Eindüsung 250 °C. Die zu beschichtenden Gegenstände (glasierte Fliesen und Glasplatten) befinden sich auf verschiedener Höhe und Anordnung im Schrank verteilt.The measured values show the excellent abrasion stability of the non-stick coatings applied by this method. Example 5 The solution from Example 1 is injected into a circulating air drying cabinet with a capacity of approximately 60 liters by means of a spray gun. The temperature of the drying cabinet during injection is 250 ° C. The objects to be coated (glazed tiles and glass plates) are distributed in the cabinet at various heights and arrangements.
Nachdem 100 ml von der Beschichtungslösung in 3 Intervallen eingedüst wurden, wird der Trok- kenschrank noch 30 Minuten bei 250 °C gehalten, dann abgeschaltet. Nat;h dem Abkühlen werden die zu beschichtenden Probekörper mit der in Beispiel 4 beschriebenen Methode auf Abriebbeständigkeit untersucht.After 100 ml of the coating solution have been injected at 3 intervals, the drying cabinet is kept at 250 ° C. for a further 30 minutes, then switched off. After cooling, the test specimens to be coated are examined for abrasion resistance using the method described in Example 4.
Figure imgf000011_0001
Figure imgf000011_0001
Das Resultat zeigt die hervorragende Abriebsstabilität der nach diesem Verfahren aufgebrachten Beschichtungen. The result shows the excellent abrasion resistance of the coatings applied by this process.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung eines Beschichtungsfluids, da- durch gekennzeichnet, daß ein hydrophiles, hydrophobes und/oder oleophobes Silan mit einem wassermischbaren Lösungsmittel versetzt, Wasser zur Vorhydrolyse zugegeben und das Vorhydrolysat verdünnt wird.1. A process for producing a coating fluid, characterized in that a hydrophilic, hydrophobic and / or oleophobic silane is mixed with a water-miscible solvent, water is added for the pre-hydrolysis and the pre-hydrolyzate is diluted.
2. Verfahren nach dem vorhergehenden Anspruch, dadurch gekennzeichnet, daß als Silan ein Alkylsilan, insbesondere fluoriertes Silan, insbesondere Tridecafluoroctyl- triethoxysilan verwendet wird.2. The method according to the preceding claim, characterized in that an alkylsilane, in particular fluorinated silane, in particular tridecafluorooctyl-triethoxysilane is used as the silane.
3. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Lösungsmittel ein Ether, Alkohol, Etheralkohol oder Keton ist.3. The method according to any one of the preceding claims, characterized in that the solvent is an ether, alcohol, ether alcohol or ketone.
4. Verfahren nach einem der vorhergehenden Ansprüche, da- durch gekennzeichnet, daß das Silan in dem wassermischbaren Lösungsmittel gelöst wird.4. The method according to any one of the preceding claims, characterized in that the silane is dissolved in the water-miscible solvent.
5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Vorhydrolyse durch Zugabe von 5 bis 50 Masse % Wasser erfolgt, insbesondere um 25 - D 'S .5. The method according to any one of the preceding claims, characterized in that the pre-hydrolysis is carried out by adding 5 to 50% by mass of water, in particular by 25 - D 'S.
6. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Vorhydrolyse bei einem sau- ren pH, insbesondere im Bereich um pH = 3 erfolgt. 6. The method according to any one of the preceding claims, characterized in that the pre-hydrolysis takes place at an acidic pH, in particular in the range around pH = 3.
7. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß als Katalysator eine Säure, insbesondere eine organische oder Mineralsäure, insbesondere Perfluoroctansäure zugesetzt wird.7. The method according to any one of the preceding claims, characterized in that an acid, in particular an organic or mineral acid, in particular perfluorooctanoic acid, is added as a catalyst.
8. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Vorhydrolyse für eine Zeit von wenigstens 5, insbesondere mindestens 10 - 30 Minuten erfolgt, insbesondere für nicht länger als Tage bis Wo- chen.8. The method according to any one of the preceding claims, characterized in that the pre-hydrolysis is carried out for a time of at least 5, in particular at least 10-30 minutes, in particular for no longer than days to weeks.
9. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß ein Silan-Feststoffgehalt zwischen 1 und 20 Prozent, insbesondere zwischen 3 und 10 Prozent gewählt wird.9. The method according to any one of the preceding claims, characterized in that a silane solids content between 1 and 20 percent, in particular between 3 and 10 percent is selected.
10. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Vorhydrolysat in Wasser verdünnt wird. 10. The method according to any one of the preceding claims, characterized in that the pre-hydrolyzate is diluted in water.
11. Verfahren nach dem vorhergehenden Anspruch, dadurch gekennzeichnet, daß ein Feststoffgehalt zwischen 0,05 und 5 %, insbesondere zwischen 0,2 und 0,8, insbesondere um 04, % Silan eingestellt wird.11. The method according to the preceding claim, characterized in that a solids content between 0.05 and 5%, in particular between 0.2 and 0.8, in particular around 04,% silane is set.
12. Verfahren zur Aufbringung einer Beschichtung mit einem12. Process for applying a coating with a
Beschichtungsfluid nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß nach der Verdünnung bis zur Verwendung eine Zeit von nicht mehr als mehreren Wochen, insbesondere weniger als 12 Wochen vergeht.Coating fluid according to one of the preceding claims, characterized in that after dilution until use a time of not more than several weeks, in particular less than 12 weeks, passes.
13. Verfahren nach dem vorhergehenden Anspruch, dadurch gekennzeichnet, daß die Aufbringung durch Fluten, Wischen, Sprühen, Schäumen erfolgt, eine Trocknung erfolgt und er- foderlichenfalls ein Nachpolieren.13. The method according to the preceding claim, characterized in that the application by flooding, wiping, Spraying, foaming, drying and, if necessary, polishing.
14. Verfahren nach dem vorhergehenden Anspruch, dadurch ge- kennzeichnet, daß der Antihafteffekt nach frühestens 1014. The method according to the preceding claim, characterized in that the non-stick effect after 10 at the earliest
Minuten ausgenutzt wird.Minutes is used.
15. Zwischenstufe des aus Vorhydrolyse nach einem der Be- schichtungsfluidherstellungsschritte erhaltenen Fluids als stabiles Zwischenprodukt, gegebenenfalls mit Zusatzstoffen. 15. Intermediate stage of the fluid obtained from pre-hydrolysis after one of the coating fluid production steps as a stable intermediate, optionally with additives.
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US9914849B2 (en) 2010-03-15 2018-03-13 Ross Technology Corporation Plunger and methods of producing hydrophobic surfaces
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US9139744B2 (en) 2011-12-15 2015-09-22 Ross Technology Corporation Composition and coating for hydrophobic performance
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