WO2004024407A1 - Procede d'impermeabilisation de la surface d'un substrat tout en conservant sa porosite - Google Patents

Procede d'impermeabilisation de la surface d'un substrat tout en conservant sa porosite Download PDF

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Publication number
WO2004024407A1
WO2004024407A1 PCT/IB2003/003680 IB0303680W WO2004024407A1 WO 2004024407 A1 WO2004024407 A1 WO 2004024407A1 IB 0303680 W IB0303680 W IB 0303680W WO 2004024407 A1 WO2004024407 A1 WO 2004024407A1
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WO
WIPO (PCT)
Prior art keywords
titanate
metal
solution
substrate
activator
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Application number
PCT/IB2003/003680
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German (de)
English (en)
Inventor
Walter Koch
Original Assignee
Nanosys Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanosys Gmbh filed Critical Nanosys Gmbh
Priority to AU2003253192A priority Critical patent/AU2003253192A1/en
Priority to EP03795121A priority patent/EP1530510A1/fr
Publication of WO2004024407A1 publication Critical patent/WO2004024407A1/fr

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Classifications

    • 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
    • C04B41/495—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
    • C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00267—Materials permeable to vapours or gases

Definitions

  • the present invention relates to a method for hydrophobizing the surface of a porous substrate while maintaining its porosity.
  • a hydrophobic barrier layer is formed on the surface of the porous substrate, which shields the substrate from the outside, but this not only reduces or prevents water absorption and / or water permeability, but also an impairment of the gas absorption capacity and / or gas permeability coated substrate.
  • Coatings of this known type take place, for example, on raw or coated surfaces of wood or wood-based materials by staining, dyeing, painting, varnishing, etc. using solvent-based and / or water-dilutable paints.
  • film-forming paints are used which, when dried, leave a more or less compact film with an average thickness of 10 to 100 ⁇ m on the coated surface.
  • the cover layer formed in this way has a moderate to good barrier effect against liquid water, while its permeability to water vapor decreases with its thickness.
  • the coating of the surface of a substrate with a hydrophobic thin layer is known, for example, from WO-98/53921: the surface to be treated is treated with reagents containing Si-H residues in the presence of an activator based on a platinum metal; in this way the surface of a non-porous substrate such as metal or glass or a porous substrate such as sandstone, concrete, wood or textile. Whether the porosity of the substrate and in particular its gas absorption capacity and / or gas permeability is maintained after the treatment is not addressed in WO-98/53921, but is more or less to be expected with the specified layer thicknesses in the range of a few nanometers. A platinum metal compound is used in this process, which is correspondingly expensive.
  • the method according to the invention forms a hydrophobic thin layer on the surface of the treated substrate as a result of the treatment of the surface with at least one reagent which contains Si-H radicals in the presence of an activator which comprises at least one metal-organic compound of a transition metal.
  • this transition metal is preferably a metal of subgroup IV or II of the periodic table, such as titanium, zirconium or zinc, and this metal-organic compound is preferably easily hydrolyzable.
  • the method according to the invention makes it possible to largely prevent the wetting of the surface of a porous substrate by water and the resultant water absorption and / or water permeability (ie to reduce it to such an extent that the surface can be regarded as non-wetted), while maintaining the Porosi- tat of the substrate, in particular its gas absorption capacity and / or gas permeability are maintained.
  • the permeability of the thin film formed to water vapor and the maintenance of the porosity of the treated substrate can essentially be explained by the thinness of the layer, while it can be assumed that the good adhesion achieved by the thin film to covalent bonds, ie to a reaction between the surface to be treated and the reagent in the presence of the activator.
  • the hydrophobic thin layer formed on the surface of the substrate by the method according to the invention remains invisible and does not noticeably or insignificantly impair the gas absorption capacity and / or gas permeability of the substrate, while nevertheless successfully hydrophobizing the surface of the substrate.
  • organic titanium compounds can be mentioned, inter alia titanium acid esters, including preferably tetrabutyl titanate (ie titanium (IV) butoxide), but also tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetraisooctyl titanate, tetrakis (2-ethylhexyl) titanate and the like, and also zirconium organic compounds, including tetrabutyl zirconate, tetra octyl zirconate, tetrakis (2,4-pentandionato) zirconate and the like.
  • Zinc-organic compounds, including dioctyl zincate can be mentioned as examples of suitable metal-organic compounds of a metal of subgroup II of the periodic table.
  • Substrates whose surface has hydroxyl, carboxyl, ammonium, amino and / or imino residues can be treated with the desired success, in particular substrates made of high molecular weight organic compounds containing the residues mentioned.
  • suitable substrates are substrates made from cellulose or cellulose derivatives or from proteins, for example wood, wood-based materials (such as chipboard, medium-density fibreboard, multilayer board, wood fiber board, cements), paper, silk, cardboard, wool, linen, flax, hemp and the like, as well as objects made from them.
  • Suitable substrates with surfaces having the abovementioned residues can also result from a surface treatment of polymers: Examples of these are substrates made of polyamide, polyethylene terephthalate and polypropylene with a pretreated, namely by corona, plasma or flame treatment and the like, or by means of strong oxidizing agents such as chromium sulfuric acid , Hydrogen peroxide and the like modified surface. Substrates that can be treated with the desired success can also occur in mixed form: for example, wood fibers, glue, papers and / or plastics can be present on the surface of wood-based materials at the same time. In addition, it is to be expected that substrates whose surface has mercapto residues can also be treated with the desired success.
  • the method according to the invention can be applied to substrates with a naturally weathered surface, and the surface of the substrate can be both planar and non-planar.
  • the use of the method according to the invention is not restricted by the size and / or nature of the surface to be treated. That is why plates, continuous foils, whole objects, inside and outside surfaces and appropriately pretreated surfaces, for example of plastics and artificial stones, can be treated with the desired success.
  • the process according to the invention is applied to polymers (in the broadest sense), if appropriate after their surface pretreatment, a wide range of properties of the treated surface can be achieved because the treated polymers in addition to the required hydroxyl, carboxyl, ammonium, amino and / or imino residues can have further functional residues and / or the pretreated polymer surfaces can be modified further, for example through oxidation, which opens up a variety of possible applications.
  • Silanes, polysilanes, siloxanes, polysilazanes, polyhydrosiloxanes, polycarbosilanes, polysiloxanes and polysilsesquioxanes can be mentioned as examples of suitable reagents containing Si-H radicals.
  • suitable reagents are solids or liquids which, as such or in a medium, are in liquid, pasty or solid form and can be used, for example, as a solution, emulsion, suspension, foam or spray.
  • the activator can be used, for example, in the form of a solid, solution, emulsion, suspension, foam, spray or other systems containing liquid and / or solid phases.
  • the activator and reagent can first be mixed together and the resulting mixture is then applied to the surface to be treated.
  • Activator and / or reagent can also first be mixed with other substances and only then applied to the surface to be treated.
  • the activator can first be applied to the surface to be treated, which is only then treated with the reagent.
  • the reverse procedure i.e. The treatment of the surface first with the reagent and then with the activator is also possible and can lead to a very deep treatment if the reagent is left over for a long time.
  • hydrophobic thin layers with different properties can be produced on the surface of the treated substrate, which in turn opens up a variety of possible uses, for example as a protective, impregnating, covering, coloring agent. , Decorative, reflection, adhesion promoter, biocompatibility, adhesive, adhesive, sliding, anti-blocking, anti-flame, non-stick, anti-graffiti, anti-fog, separating and / or demolding layers.
  • the energy of the hydrophobic thin layers formed can be varied so that, for example, differently wettable hydrophilic, oleophilic, hydrophobic or oleophobic thin layers can be produced with different contact angles.
  • the method according to the invention enables their surface modification with corresponding applications in the protection or renovation of buildings, monuments and / or works of art, as well as in various areas of the construction, automotive and machine industries.
  • the method according to the invention enables the formation of well-adhering, weather-resistant, colorless and invisible, water-impermeable but water-vapor-permeable thin layers (which can be hydrophobic or hydrophilic, or oleophobic or oleophilic) directly on the wood or on wood surfaces previously coated with organic substances, for example on raw, stained, glazed, impregnated or lacquered surfaces of wood and wood-based materials such as medium-density fibreboard, chipboard, multi-layer board, wood fiber cement, which can then be used indoors or outdoors.
  • the method according to the invention can also be used for fungicide-free protective treatment (preservation and / or preservation) of wood.
  • the method according to the invention can be combined with other treatments in order to achieve or intensify effects of the type mentioned above.
  • the good adhesion of the thin layer to the treated surface of the substrate in combination with the properties of the thin layer itself that can be achieved on its free surface result in a wide variety of applications, including for the thermal application of plastics which are sprayed directly onto the treated surface or can be injected, or for non-stick finishing of wooden cement boards, for antigraffiti treatment, for fungicide treatment, for biocide treatment, for the treatment of skiing surfaces and the like.
  • the following examples illustrate individual aspects of the invention, the method according to the invention being used under room conditions. However, the method according to the invention can also be carried out without problems under other atmospheric conditions, for example under carbon dioxide, nitrogen, etc. at temperatures other than room temperature and under pressure or vacuum.
  • Solid beech served as substrate.
  • a 5% solution of hydride-terminated polysiloxane with a molecular weight of 26,000 in butyl acetate 98/100 was used as the reagent.
  • a 1% solution of tetrabutyl titanate in toluene was used as the activator.
  • the mixing ratio was 8% tetrabutyl titanate solid per 100 parts of polysiloxane. 10 g / m 2 of the reaction liquid were applied by brushing. After drying overnight at room temperature, the water wetting behavior was examined by dripping on distilled water for two hours: the treated surface could not be wetted.
  • Example 2 Solid spruce served as substrate.
  • the mixing ratio was 8 parts tetrabutyl titanate solid to 100 parts polysiloxane. 10 g / m 2 of the reaction liquid were applied by brushing. After drying overnight at room temperature, the water wetting behavior was examined by dripping on distilled water for two hours: the treated surface could not be wetted.
  • Example 3 Solid spruce served as a substrate, radial cut.
  • a 5% solution of hydride-terminated polysiloxane 40 mPas with an Si content of 4.2 mmol / g in ethyl acetate was used as the reagent.
  • a 1% solution of tetrabutyl titanate in butyl acetate 98/100 was used as an activator.
  • the mixing ratio was 10 parts tetrabutyl titanate solid to 100 parts polysiloxane. 10 g / m 2 of the reaction liquid were applied by brushing. After drying overnight at room temperature, the water wetting behavior was examined by dripping on distilled water for two hours: the treated end grain wood surface could not be wetted.
  • a medium-density fibreboard with a thickness of 19 mm served as the substrate.
  • Reagent was a 10% solution of trimethylsilyl-terminated polysiloxane 45 mPAs in ethyl acetate techn. A 1% solution of tetrabutyl titanate in ethyl acetate was used as the activator. The mixing ratio was 10 parts tetrabutyl titanate solid to 100 parts polysiloxane. 20 g / m 2 of the reaction liquid were applied by brushing. After drying overnight at room temperature, the water wetting behavior was examined by dripping on distilled water for two hours: the treated surface of the medium-density fiberboard could not be wetted either on the cut edge or on the surface.
  • Example 5 A pure silk tie painted with silk paints served as the substrate.
  • a 5% solution of trimethylsilyl-terminated polysiloxane 45 mPAs with 7.8 mmol / g Si-H content in ethyl acetate was used as the reagent.
  • a 1% solution of tetrabutyl titanate in ethyl acetate was used as the activator.
  • the mixing ratio was 5 parts tetrabutyl titanate solid to 100 parts polysiloxane. 10 g / m 2 of the reaction liquid were applied by brushing. After drying overnight at room temperature, the wetting behavior of red wine of 12.0% alcohol by dripping was examined: the treated silk tie surface did not absorb the test reagent and remained free of stains.
  • a 13 mm thick chipboard was used as the substrate.
  • a 10% solution of trimethylsilyl-terminated polysiloxane 100 mPAs with 3.8 mmol / g Si-H content in naphtha (bp approx. 130-160 ° C.) was used as the reagent.
  • the activator served a 1% solution of tetrabutyl titanate in white spirit freed from aromatic compounds.
  • the mixing ratio was 7 parts tetrabutyl titanate solid to 100 parts polysiloxane.
  • 20 g / m 2 of the reaction liquid were applied by brushing. After drying overnight at room temperature, the water wetting behavior was examined by dripping on distilled water for two hours: the treated chipboard could not be wetted either on the surface or on the cut edge.
  • Example 8 An impregnated and dark red-brown, solvent-containing spruce board of unknown origin, which had been impregnated and glazed with an oil / alkyd resin glaze, was used as the substrate and was exposed to the weather for 5 years.
  • a 5% solution of trimethylsilyl-terminated polysiloxane 500 mPAs with 2.1 mmol / g Si-H content in naphtha (bp. Approx. 130-160 ° C.) was used as the reagent.
  • a 1% solution of tetrabutyl titanate in white spirit freed from aromatic compounds served as the activator.
  • the mixing ratio was 7 parts tetrabutyl titanate solid to 100 parts polysiloxane.
  • Exposed sandstone of the "rorschacher sandstone" type served as the substrate.
  • a 10% solution of dimethylsiloxane-methylhydrogensiloxane copolymer 45 mPas in butyl acetate 98/100 was used as the reagent.
  • a 1% solution of tetrabutyl titanate in toluene was used as the activator.
  • the mixing ratio was 7% solid tetrabutyl titanate per 100 parts of polysiloxane.
  • 30 g / m 2 of the reaction liquid were applied by spraying. After drying overnight, the water wetting behavior was examined by spraying with tap water: the treated surface could not be wetted.
  • a fiber cement facade painted with a solvent-based facade paint based on acrylate served as the substrate.
  • a 5% solution of Si-H-terminated polydimethylsiloxane 500 mPas in butyl acetate 98/100 was used as the reagent.
  • a 1% solution of tetrabutyl titanate in white spirit with 18% by weight of aromatic compounds served as the activator.
  • the mixing ratio was 10% solid to 100 parts of polysiloxane. 50 g / m 2 of the reaction liquid were applied by spraying. After drying overnight, the water Wetting behavior examined by spraying with tap water: The treated surface could not be wetted.
  • Example 12 A weathered shutter, painted with a silicone alkyd resin paint, served as the substrate.
  • a 5% solution of Si-H-terminated polydimethylsiloxane 3 cSt in butyl acetate 98/100 was used as the reagent.
  • a 1% solution of tetrabutyl titanate in white spirit with 18% by weight of aromatic compounds served as the activator.
  • the mixing ratio was 7% solid tetrabutyl titanate per 100 parts of polysiloxane. 50 g / m 2 of the reaction liquid were applied by spraying. After drying overnight, the water wetting behavior was examined by spraying with tap water: the treated surface could not be wetted.
  • a tennis ball of an unknown brand served as the substrate.
  • a 5% solution of Si-H-terminated polydimethylsiloxane 100 cSt in butyl acetate 98/100 was used as the reagent.
  • a 1% solution of tetrabutyl titanate in white spirit with 18% by weight of aromatic compounds served as the activator.
  • the mixing ratio was 7% solid tetrabutyl titanate per 100 parts of polysiloxane. 10 g of the reaction liquid were applied uniformly over the surface by spraying. After drying overnight, the water wetting behavior was examined by submerging it several times in tap water: the treated tennis ball did not get wet.
  • An interior plaster served as the substrate.
  • a 5% solution of Si-H-terminated polydimethylsiloxane 500 cSt in butyl acetate 98/100 was used as the reagent.
  • a 1% solution of tetrabutyl titanate in white spirit with 18% by weight of aromatic compounds served as the activator.
  • the mixing ratio was 7% solid tetrabutyl titanate per 100 parts of polysiloxane.
  • Oak parquet pieces served as the substrate.
  • a 5% solution of Si-H-terminated polydimethylsiloxane 1000 cSt in butyl acetate 98/100 was used as the reagent.
  • a 1% solution of tetrabutyl titanate in toluene was used as the activator.
  • the mixing ratio was 8% tetrabutyl titanate solid per 100 parts of polysiloxane.
  • 20 g / m 2 of the reaction liquid were applied to the cut edges by spraying. After drying overnight at room temperature, the water wetting behavior of the cut edges was examined by dripping on distilled water for 30 minutes: the treated surface could not be wetted.
  • Maple parquet straps served as the substrate.
  • a 5% solution of hydride-terminated polysiloxane with a molecular weight of 26,000 in butyl acetate 98/100 was used as the reagent.
  • a 1% solution of tetrabutyl titanate in toluene was used as the activator.
  • the mixing ratio was 8% tetrabutyl titanate solid per 100 parts of polysiloxane.
  • 20 g / m 2 of the reaction liquid were applied to the cut edges by spraying. After drying overnight at room temperature, the water wetting behavior of the cut edges was examined by dripping on distilled water for 30 minutes: the treated surface could not be wetted.
  • Beech parquet straps served as the substrate.
  • a 5% solution of hydride-terminated polysiloxane with a molecular weight of 26,000 in butyl acetate 98/100 was used as the reagent.
  • a 1% solution of tetrabutyl titanate in toluene was used as the activator.
  • the mixing ratio was 8% tetrabutyl titanate solid per 100 parts of polysiloxane.
  • 20 g / m 2 of the reaction liquid were applied to the cut edges by spraying. After drying overnight at room temperature, the wetting behavior the cut edges were examined by brushing on a water-thinnable parquet sealing lacquer: the parquet lacquer did not adhere to the treated surface.
  • Cross-sections of pine branches served as the substrate.
  • a 10% solution of hydride-terminated polysiloxane of molecular weight 26,000 in xylene was used as the reagent.
  • a 1% solution of tetrabutyl titanate in toluene was used as the activator.
  • the mixing ratio was 7% solid tetrabutyl titanate to 100 parts polysiloxane.
  • 50 g / m 2 of the reaction liquid were applied to the cut edges by spraying. After drying overnight at room temperature, the wetting behavior of the cut edges was investigated by dripping tap water: the treated surface could not be wetted.
  • Solid spruce served as the substrate.
  • a 5% solution of hydride-terminated polysiloxane with a molecular weight of 26,000 in toluene was used as the reagent.
  • a 1% solution of tetrabutyl titanate in xylene was used as an activator.
  • the mixing ratio was 8 parts tetrabutyl titanate solid to 100 parts polysiloxane.
  • the spruce test specimens were immersed in the reaction liquid for 5 seconds. After drying overnight at room temperature, the water wetting behavior was examined by dripping on distilled water for two hours: the treated surface could not be wetted.
  • Solid ash served as the substrate.
  • a 5% solution of hydride-terminated polysiloxane with a molecular weight of 26,000 in toluene was used as the reagent.
  • a 1% solution of tetrabutyl titanate in xylene was used as an activator.
  • the mixing ratio was 8 parts tetrabutyl titanate solid to 100 parts polysiloxane.
  • the ash test specimens were immersed in the reaction liquid for 10 seconds. After drying overnight at room temperature, the water wetting behavior was determined by dripping on distillation Water was examined for two hours: the treated surface could not be wetted.
  • Example 21 A raw blockboard was used as the substrate.
  • a 5% solution of hydride-terminated polysiloxane with a molecular weight of 26,000 in toluene was used as the reagent.
  • a 1% solution of tetrabutyl titanate in xylene was used as an activator.
  • the mixing ratio was 8 parts tetrabutyl titanate solid to 100 parts polysiloxane.
  • the block board was once brushed with the reaction liquid. After drying overnight at room temperature, the water wetting behavior was examined by dripping on distilled water for two hours: the treated surface could not be wetted.
  • a new concrete control panel served as the substrate.
  • a 5% solution of hydride-terminated polysiloxane with a molecular weight of 26,000 in toluene was used as the reagent.
  • a 1% solution of tetrabutyl titanate in xylene was used as an activator.
  • the mixing ratio was 8 parts tetrabutyl titanate solid to 100 parts polysiloxane.
  • the control panel was brushed once on all sides with the reaction liquid. After drying overnight at room temperature, the water wetting behavior was examined by dripping on distilled water for two hours: the treated surface could not be wetted.
  • a new precision control panel served as the substrate.
  • a 5% solution of hydride-terminated polysiloxane with a molecular weight of 26,000 in toluene was used as the reagent.
  • a 1% solution of tetrabutyl titanate in xylene was used as the activator.
  • the mixing ratio was 8 parts tetrabutyl titanate solid to 100 parts polysiloxane.
  • the control panel was brushed once on all sides with the reaction liquid. After drying overnight at room temperature, the water wetting behavior was determined by dripping on distilled water examined for two hours: the treated surface could not be wetted.
  • Example 24 Nordic spruce, radial cut, solid served as substrate.
  • the mixing ratio was 8% tetrakis (2,4-pentanedionato) zirconate solid to 100 parts of polysiloxane.
  • 40 g / m 2 of the reaction liquid were applied by brushing. After drying overnight at room temperature, the water wetting behavior was examined by dripping on distilled water for two hours: the treated surface could not be wetted.
  • Example 29 Nordic spruce, radial cut, solid served as substrate.
  • a 5% solution of hydride-terminated polysiloxane with a molecular weight of 26,000 in naphtha (bp. Approx. 130-160 ° C.) was used as the reagent.
  • a 1% solution of tetraisopropyl titanate in toluene was used as the activator.
  • the mixing ratio was 8% solid tetraisopropyl titanate per 100 parts of lysiloxan. 40 g / m 2 of the reaction liquid were applied by brushing. After drying overnight at room temperature, the water wetting behavior was examined by dripping on distilled water for two hours: the treated surface could not be wetted.
  • Example 31 Nordic spruce, radial cut, solid served as substrate.
  • a 5% solution of hydride-terminated polysiloxane with a molecular weight of 26,000 in naphtha (bp. Approx. 130-160 ° C.) was used as the reagent.
  • a 1% solution of tetraisooctyl titanate in toluene was used as an activator.
  • the mixing ratio was 8% solid tetraisooctyl titanate per 100 parts polysiloxane.
  • 40 g / m 2 of the reaction liquid were applied by brushing. After drying overnight at room temperature, the water wetting behavior was examined by dripping on distilled water for two hours: the treated surface could not be wetted.
  • concentrations and times given in the examples given above were chosen so that practical conditions for coating a surface, for example with an impregnating were simulated with it.
  • the method according to the invention can also be carried out with other concentrations, application quantities and / or exposure times.
  • the coating was carried out by brushing, spraying, spraying or dipping.
  • the coating can also be carried out in another way, for example by flooding, misting, gassing, rolling, printing or rolling.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

Selon l'invention, au moins un réactif contenant des restes Si-H est mis en contact avec la surface à imperméabiliser du substrat en présence d'un activateur qui contient au moins un composé organo-métallique des sous-groupes IV et II de la classification périodique des éléments. Le composé organo-métallique est sélectionné, de préférence, parmi des composés organiques de titane, de zirconium et de zinc et peut être notamment un ester d'acide de titane sélectionné parmi le tétrabutyle de titane, tétra-éthyle de titane, tétrapropyle de titane, tétra-isopropyle de titane, tétra-isooctyle de titane et tétrakis(2-éthylhexyl)titane, un ester d'acide de zirconimum sélectionné notamment parmi le tétrabutyle de zirconate, tétraoctyle de zirconate et tétrakis(2,4pentandionato)zirconate ou un ester d'acide de zinc comme le dioctyle de zinkate. Le composé ograno-métallique est, de préférence, facile à hydrolyser.
PCT/IB2003/003680 2002-08-27 2003-08-15 Procede d'impermeabilisation de la surface d'un substrat tout en conservant sa porosite WO2004024407A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2003253192A AU2003253192A1 (en) 2002-08-27 2003-08-15 Method for applying a hydrophobic coating to the surface of a porous substrate, maintaining its porosity
EP03795121A EP1530510A1 (fr) 2002-08-27 2003-08-15 Procede d'impermeabilisation de la surface d'un substrat tout en conservant sa porosite

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH14632002 2002-08-27
CH20021463/02 2002-08-27

Publications (1)

Publication Number Publication Date
WO2004024407A1 true WO2004024407A1 (fr) 2004-03-25

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US7195733B2 (en) 2004-04-27 2007-03-27 The Board Of Trustees Of The University Of Illinois Composite patterning devices for soft lithography
US7521292B2 (en) 2004-06-04 2009-04-21 The Board Of Trustees Of The University Of Illinois Stretchable form of single crystal silicon for high performance electronics on rubber substrates
US7557367B2 (en) 2004-06-04 2009-07-07 The Board Of Trustees Of The University Of Illinois Stretchable semiconductor elements and stretchable electrical circuits
US7799699B2 (en) 2004-06-04 2010-09-21 The Board Of Trustees Of The University Of Illinois Printable semiconductor structures and related methods of making and assembling
CN101121824B (zh) * 2005-08-12 2011-04-20 纳米技术陶瓷株式会社 用于聚合物组合物基体的粘合增强剂和含有该粘合增强剂的聚合物组合物
US7943491B2 (en) 2004-06-04 2011-05-17 The Board Of Trustees Of The University Of Illinois Pattern transfer printing by kinetic control of adhesion to an elastomeric stamp
US8504305B2 (en) 1998-12-17 2013-08-06 Hach Company Anti-terrorism water quality monitoring system
US8865489B2 (en) 2009-05-12 2014-10-21 The Board Of Trustees Of The University Of Illinois Printed assemblies of ultrathin, microscale inorganic light emitting diodes for deformable and semitransparent displays
US8886334B2 (en) 2008-10-07 2014-11-11 Mc10, Inc. Systems, methods, and devices using stretchable or flexible electronics for medical applications
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US9056783B2 (en) 1998-12-17 2015-06-16 Hach Company System for monitoring discharges into a waste water collection system
US9117940B2 (en) 2007-01-17 2015-08-25 The Board Of Trustees Of The University Of Illinois Optical systems fabricated by printing-based assembly
US9159635B2 (en) 2011-05-27 2015-10-13 Mc10, Inc. Flexible electronic structure
US9171794B2 (en) 2012-10-09 2015-10-27 Mc10, Inc. Embedding thin chips in polymer
US9289132B2 (en) 2008-10-07 2016-03-22 Mc10, Inc. Catheter balloon having stretchable integrated circuitry and sensor array
US9324733B2 (en) 2004-06-04 2016-04-26 The Board Of Trustees Of The University Of Illinois Controlled buckling structures in semiconductor interconnects and nanomembranes for stretchable electronics
US9442285B2 (en) 2011-01-14 2016-09-13 The Board Of Trustees Of The University Of Illinois Optical component array having adjustable curvature
US9554484B2 (en) 2012-03-30 2017-01-24 The Board Of Trustees Of The University Of Illinois Appendage mountable electronic devices conformable to surfaces
US9691873B2 (en) 2011-12-01 2017-06-27 The Board Of Trustees Of The University Of Illinois Transient devices designed to undergo programmable transformations
CN106965273A (zh) * 2017-04-17 2017-07-21 南京林业大学 利用常压等离子体改性塑料薄膜制备环保胶合板的方法
US9723122B2 (en) 2009-10-01 2017-08-01 Mc10, Inc. Protective cases with integrated electronics
US9765934B2 (en) 2011-05-16 2017-09-19 The Board Of Trustees Of The University Of Illinois Thermally managed LED arrays assembled by printing
CN107236546A (zh) * 2017-06-23 2017-10-10 河北麦森钛白粉有限公司 与植物和/或微生物联用的土壤修复促进剂的制备方法
US9936574B2 (en) 2009-12-16 2018-04-03 The Board Of Trustees Of The University Of Illinois Waterproof stretchable optoelectronics
US9986924B2 (en) 2010-03-17 2018-06-05 The Board Of Trustees Of The University Of Illinois Implantable biomedical devices on bioresorbable substrates
US10441185B2 (en) 2009-12-16 2019-10-15 The Board Of Trustees Of The University Of Illinois Flexible and stretchable electronic systems for epidermal electronics
WO2020165387A1 (fr) 2019-02-14 2020-08-20 Umicore Ag & Co. Kg Procédé pour la fabrication de catalyseurs de gaz d'échappement de véhicule
US10918298B2 (en) 2009-12-16 2021-02-16 The Board Of Trustees Of The University Of Illinois High-speed, high-resolution electrophysiology in-vivo using conformal electronics
US10925543B2 (en) 2015-11-11 2021-02-23 The Board Of Trustees Of The University Of Illinois Bioresorbable silicon electronics for transient implants
US20210095152A1 (en) * 2017-11-30 2021-04-01 Hewlett-Packard Development Company, L.P. Three-dimensional printing
US11029198B2 (en) 2015-06-01 2021-06-08 The Board Of Trustees Of The University Of Illinois Alternative approach for UV sensing
US11118965B2 (en) 2015-06-01 2021-09-14 The Board Of Trustees Of The University Of Illinois Miniaturized electronic systems with wireless power and near-field communication capabilities

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FR1181813A (fr) * 1956-08-31 1959-06-18 Union Chimique Belge Sa Compositions pour rendre hydrophobes des matières poreuses ou fibreuses
DE1936712A1 (de) * 1968-07-20 1970-03-05 Kanegafuchi Spinning Co Ltd Verfahren zur Herstellung von Faserstrukturen mit einer vorzueglichen Dehnungsrueckbildung
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US8504305B2 (en) 1998-12-17 2013-08-06 Hach Company Anti-terrorism water quality monitoring system
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US9069927B2 (en) 1998-12-17 2015-06-30 Hach Company Anti-terrorism water quality monitoring system
US9056783B2 (en) 1998-12-17 2015-06-16 Hach Company System for monitoring discharges into a waste water collection system
US9015003B2 (en) 1998-12-17 2015-04-21 Hach Company Water monitoring system
US8958917B2 (en) 1998-12-17 2015-02-17 Hach Company Method and system for remote monitoring of fluid quality and treatment
US8577623B2 (en) 1998-12-17 2013-11-05 Hach Company Anti-terrorism water quality monitoring system
US8920619B2 (en) 2003-03-19 2014-12-30 Hach Company Carbon nanotube sensor
US9739742B2 (en) 2003-03-19 2017-08-22 Hach Company Carbon nanotube sensor
US7195733B2 (en) 2004-04-27 2007-03-27 The Board Of Trustees Of The University Of Illinois Composite patterning devices for soft lithography
US7799699B2 (en) 2004-06-04 2010-09-21 The Board Of Trustees Of The University Of Illinois Printable semiconductor structures and related methods of making and assembling
US11456258B2 (en) 2004-06-04 2022-09-27 The Board Of Trustees Of The University Of Illinois Stretchable form of single crystal silicon for high performance electronics on rubber substrates
US9450043B2 (en) 2004-06-04 2016-09-20 The Board Of Trustees Of The University Of Illinois Methods and devices for fabricating and assembling printable semiconductor elements
US11088268B2 (en) 2004-06-04 2021-08-10 The Board Of Trustees Of The University Of Illinois Methods and devices for fabricating and assembling printable semiconductor elements
US10355113B2 (en) 2004-06-04 2019-07-16 The Board Of Trustees Of The University Of Illinois Controlled buckling structures in semiconductor interconnects and nanomembranes for stretchable electronics
US9515025B2 (en) 2004-06-04 2016-12-06 The Board Of Trustees Of The University Of Illinois Stretchable form of single crystal silicon for high performance electronics on rubber substrates
US7943491B2 (en) 2004-06-04 2011-05-17 The Board Of Trustees Of The University Of Illinois Pattern transfer printing by kinetic control of adhesion to an elastomeric stamp
US10204864B2 (en) 2004-06-04 2019-02-12 The Board Of Trustees Of The University Of Illinois Stretchable form of single crystal silicon for high performance electronics on rubber substrates
US7622367B1 (en) 2004-06-04 2009-11-24 The Board Of Trustees Of The University Of Illinois Methods and devices for fabricating and assembling printable semiconductor elements
US7557367B2 (en) 2004-06-04 2009-07-07 The Board Of Trustees Of The University Of Illinois Stretchable semiconductor elements and stretchable electrical circuits
US9105555B2 (en) 2004-06-04 2015-08-11 The Board Of Trustees Of The University Of Illinois Stretchable form of single crystal silicon for high performance electronics on rubber substrates
US9768086B2 (en) 2004-06-04 2017-09-19 The Board Of Trustees Of The University Of Illinois Methods and devices for fabricating and assembling printable semiconductor elements
US9761444B2 (en) 2004-06-04 2017-09-12 The Board Of Trustees Of The University Of Illinois Methods and devices for fabricating and assembling printable semiconductor elements
US10374072B2 (en) 2004-06-04 2019-08-06 The Board Of Trustees Of The University Of Illinois Methods and devices for fabricating and assembling printable semiconductor elements
US7521292B2 (en) 2004-06-04 2009-04-21 The Board Of Trustees Of The University Of Illinois Stretchable form of single crystal silicon for high performance electronics on rubber substrates
US9324733B2 (en) 2004-06-04 2016-04-26 The Board Of Trustees Of The University Of Illinois Controlled buckling structures in semiconductor interconnects and nanomembranes for stretchable electronics
CN101121824B (zh) * 2005-08-12 2011-04-20 纳米技术陶瓷株式会社 用于聚合物组合物基体的粘合增强剂和含有该粘合增强剂的聚合物组合物
US10361180B2 (en) 2007-01-17 2019-07-23 The Board Of Trustees Of The University Of Illinois Optical systems fabricated by printing-based assembly
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US8905772B2 (en) 2008-03-05 2014-12-09 The Board Of Trustees Of The University Of Illinois Stretchable and foldable electronic devices
US10292261B2 (en) 2008-03-05 2019-05-14 The Board Of Trustees Of The University Of Illinois Stretchable and foldable electronic devices
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US8946683B2 (en) 2008-06-16 2015-02-03 The Board Of Trustees Of The University Of Illinois Medium scale carbon nanotube thin film integrated circuits on flexible plastic substrates
US8886334B2 (en) 2008-10-07 2014-11-11 Mc10, Inc. Systems, methods, and devices using stretchable or flexible electronics for medical applications
US9289132B2 (en) 2008-10-07 2016-03-22 Mc10, Inc. Catheter balloon having stretchable integrated circuitry and sensor array
US9012784B2 (en) 2008-10-07 2015-04-21 Mc10, Inc. Extremely stretchable electronics
US10546841B2 (en) 2009-05-12 2020-01-28 The Board Of Trustees Of The University Of Illinois Printed assemblies of ultrathin, microscale inorganic light emitting diodes for deformable and semitransparent displays
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US8865489B2 (en) 2009-05-12 2014-10-21 The Board Of Trustees Of The University Of Illinois Printed assemblies of ultrathin, microscale inorganic light emitting diodes for deformable and semitransparent displays
US9723122B2 (en) 2009-10-01 2017-08-01 Mc10, Inc. Protective cases with integrated electronics
US9936574B2 (en) 2009-12-16 2018-04-03 The Board Of Trustees Of The University Of Illinois Waterproof stretchable optoelectronics
US10918298B2 (en) 2009-12-16 2021-02-16 The Board Of Trustees Of The University Of Illinois High-speed, high-resolution electrophysiology in-vivo using conformal electronics
US11057991B2 (en) 2009-12-16 2021-07-06 The Board Of Trustees Of The University Of Illinois Waterproof stretchable optoelectronics
US10441185B2 (en) 2009-12-16 2019-10-15 The Board Of Trustees Of The University Of Illinois Flexible and stretchable electronic systems for epidermal electronics
US9986924B2 (en) 2010-03-17 2018-06-05 The Board Of Trustees Of The University Of Illinois Implantable biomedical devices on bioresorbable substrates
US9442285B2 (en) 2011-01-14 2016-09-13 The Board Of Trustees Of The University Of Illinois Optical component array having adjustable curvature
US9765934B2 (en) 2011-05-16 2017-09-19 The Board Of Trustees Of The University Of Illinois Thermally managed LED arrays assembled by printing
US9159635B2 (en) 2011-05-27 2015-10-13 Mc10, Inc. Flexible electronic structure
US10349860B2 (en) 2011-06-03 2019-07-16 The Board Of Trustees Of The University Of Illinois Conformable actively multiplexed high-density surface electrode array for brain interfacing
US8934965B2 (en) 2011-06-03 2015-01-13 The Board Of Trustees Of The University Of Illinois Conformable actively multiplexed high-density surface electrode array for brain interfacing
US10396173B2 (en) 2011-12-01 2019-08-27 The Board Of Trustees Of The University Of Illinois Transient devices designed to undergo programmable transformations
US9691873B2 (en) 2011-12-01 2017-06-27 The Board Of Trustees Of The University Of Illinois Transient devices designed to undergo programmable transformations
US9554484B2 (en) 2012-03-30 2017-01-24 The Board Of Trustees Of The University Of Illinois Appendage mountable electronic devices conformable to surfaces
US10357201B2 (en) 2012-03-30 2019-07-23 The Board Of Trustees Of The University Of Illinois Appendage mountable electronic devices conformable to surfaces
US10052066B2 (en) 2012-03-30 2018-08-21 The Board Of Trustees Of The University Of Illinois Appendage mountable electronic devices conformable to surfaces
US9171794B2 (en) 2012-10-09 2015-10-27 Mc10, Inc. Embedding thin chips in polymer
US11029198B2 (en) 2015-06-01 2021-06-08 The Board Of Trustees Of The University Of Illinois Alternative approach for UV sensing
US11118965B2 (en) 2015-06-01 2021-09-14 The Board Of Trustees Of The University Of Illinois Miniaturized electronic systems with wireless power and near-field communication capabilities
US10925543B2 (en) 2015-11-11 2021-02-23 The Board Of Trustees Of The University Of Illinois Bioresorbable silicon electronics for transient implants
CN106965273A (zh) * 2017-04-17 2017-07-21 南京林业大学 利用常压等离子体改性塑料薄膜制备环保胶合板的方法
CN107236546B (zh) * 2017-06-23 2019-07-23 河北麦森钛白粉有限公司 与植物和/或微生物联用的土壤修复促进剂的制备方法
CN107236546A (zh) * 2017-06-23 2017-10-10 河北麦森钛白粉有限公司 与植物和/或微生物联用的土壤修复促进剂的制备方法
US20210095152A1 (en) * 2017-11-30 2021-04-01 Hewlett-Packard Development Company, L.P. Three-dimensional printing
WO2020165387A1 (fr) 2019-02-14 2020-08-20 Umicore Ag & Co. Kg Procédé pour la fabrication de catalyseurs de gaz d'échappement de véhicule
DE102019103765B4 (de) 2019-02-14 2023-01-12 Umicore Ag & Co. Kg Verfahren zur Herstellung von Autoabgaskatalysatoren

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