Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B08—CLEANING
  • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
  • B08B17/00—Methods preventing fouling
  • B08B17/02—Preventing deposition of fouling or of dust
  • B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B08—CLEANING
  • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
  • B08B17/00—Methods preventing fouling
  • B08B17/02—Preventing deposition of fouling or of dust
  • B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
  • B08B17/065—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
• • 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
  • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
  • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
• • 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
  • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
  • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
  • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
• • 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
  • C03C2217/40—Coatings comprising at least one inhomogeneous layer

Definitions

• the invention relates to a method for producing a product with an easily cleanable surface by coating the surface with a hydrophobic material, and to the products obtainable by the method.
• the equipping of objects with dirt-repellent substances is generally known.
• the usual procedure is to hydrophobize the surface of the objects to be treated by applying a liquid composition.
• a large number of chemicals are usually used for this, but in particular silicone oils and / or fluorinated silanes.
• the surfaces treated in this way prove to be difficult to wet, causing the water to roll off. Dirt adheres only weakly to the treated surface and is therefore easy to remove.
• EP-A-0, 658, 525 describes the production of a water-repellent multilayer film.
• Three different target solutions are prepared, mixed, applied to a glass substrate and a gel coating is created on the glass surface.
• a metal oxide surface layer is then produced by heating.
• a fluoroalkylsilane layer is then applied to this metal oxide layer, as described above.
• JP-A-11 092 175 describes a process according to which methoxysilane or an ethoxysilane compound containing a fluorocarbon chain is fixed on the surface of small particles with a diameter of 100 nm.
• the particles modified in this way are then dissolved in an aqueous medium and applied to a surface to be coated, the solvent is removed and the residue is then baked. In this way a surface coated with small hydrophobized particles is obtained.
• WO 99/64363 describes the production of a water-repellent surface, the surface of the glass first being roughened and all metal ions present on the surface being removed. A water-repellent film is then applied to the previously treated surface in a manner known per se. By roughening the surface, the roughness valleys thus obtained are filled with the hydrophobicizing agent.
• WO 99/02463 describes the production of a scratch-resistant coating in which an organic substance with silicone-like networks is applied to the surface. Subsequently, a heat treatment is carried out at which the temperature and duration are selected such that the applied, purely organic layer is largely decomposed and / or removed, but a connection of inorganic molecules of the carrier material and organic molecules of the applied substance can form in the uppermost molecular layers. In this way, an organic substance, such as a methyl group, is bonded directly to the silicon atom of the glass surface, forming an Si-C bond.
• the aim of the invention is therefore to provide an easy-care object whose easy-care and dirt-repellent finish remains permanently and which is also abrasion-resistant under stress, as a result of which the aforementioned easy-care properties on the object or product are retained for a long time.
• Another object of the invention is to provide such equipment for optical elements which does not change the optical properties of the element or does not noticeably change it.
• a uniform, resistant coating or a coating on a product with homogeneous properties in cross section can be achieved by providing its surface with a layer which comprises a thin metal oxide network or a metal oxide matrix, in the network a hydrophobic substance is evenly distributed.
• the layer is usually a uniform layer made of a coherent sheet-like metal oxide network.
• the metal oxide networks according to the invention can have open or closed pores.
• the metal oxide layers according to the invention are formed by thermal treatment of an applied gel layer and remain on the product as a solid coating or coating.
• the hydrophobic substance is present in the coating according to the invention in an evenly distributed manner, that is to say from the layer side adhering to the carrier material to the outer layer surface over the cross section in a homogeneous concentration and does not accumulate, exclusively or mainly on the outer coating surface.
• the surface layer retains the properties desired according to the invention even in the case of surface abrasion.
• the gels used according to the invention are in particular metal oxide gels which can be produced by means of a sol-gel process.
• the gels are formed in situ during application to the object or product to be coated, as a result of which a uniform, continuous gel network is generated on the surface of the object to be coated.
• Preferred metal oxides are Si0 2 / A1 2 0 3 , Fe 2 0 3 , In 2 0 3 , Sn0 2 , Zr0 2 , B 2 0 4 and / or Ti0 2 .
• Preferred gels are hydrogels, alkogels, xerogels and / or aerogels.
• the inventive addition of the hydrophobic, possibly also oleophobic, substance to the sol mixture before or during the formation of the gel has the effect that the hydrophobic substance is contained in an evenly distributed manner in the entire volume of the gel network being formed and is chemically bound, for example, by its silanol groups by polycondensation , In this way it is possible to impart particularly abrasion-resistant and permanent dirt-repellent properties to the surface treated in this way.
• the general production of gel layers by means of a sol-gel process is known per se and has been described in many different ways.
• the usual procedure is that in a solution, preferably a water-containing and / or alcoholic solution, with inorganic metal salts or organometallic compounds such as metal alkoxides, a polymer reaction is produced by hydrolysis, a colloidal suspension, ie a sol, being formed.
• a continuous gel network is formed from the sol by further hydrolysis.
• the formation of the gel is preferably generated directly during the coating.
• the final formation of the entire gel network is preferably accelerated by heating. Typical temperatures for this are between 0 ° C. and 200 ° C., preferably between 20 ° C.
• the hydrolysis with formation of the sol is usually started with an excess of distilled water and by standing for a longer period, for example two to four days, is carried out at ambient temperature and if necessary. the sol is formed even at elevated temperature.
• hydrophobic substances that can be stored in the forming gel are suitable as hydrophobic substances.
• hydrophobic substances which are distributed as evenly as possible in the gel-forming sol solution.
• the hydrophobic substances used in the process according to the invention are therefore preferably themselves to a small extent water-soluble or can be made water-soluble by means of solubilizers or by hydrolysis.
• the oleophobic substances used according to the invention have a chemical modification which imparts water solubility. Such modifications are water-soluble groups such as amino groups or acid groups.
• silicone oils and / or longer-chain fatty acids examples include natural and synthetic oils and / or longer-chain fatty acids, in particular fatty acids with a chain with at least 6 carbon atoms, preferably at least 10 carbon atoms.
• hydrophobic oleophobic substances in particular silicones and silanes, siloxanes, silicone oils, silicone greases, are particularly preferred.
• the silicone compounds used according to the invention can be straight-chain or branched or, if appropriate, also contain cyclic silane groups. In a preferred embodiment, they contain a water-solubilizing function, such as an amino group, the hydrogen atoms of which may also be substituted.
• the hydrophobic substances used according to the invention are preferably fluorine-containing and in particular have at least 5%, preferably at least 10%, fluorine atoms (based on the total number of atoms of the hydrophobic substance that has been incorporated after sintering). However, they preferably have at least 20% fluorine atoms, with at least 30% being particularly preferred.
• fluorine atoms based on the total number of atoms of the hydrophobic substance that has been incorporated after sintering.
• they preferably have at least 20% fluorine atoms, with at least 30% being particularly preferred.
• Hydrophobic materials with methoxy, ethoxy, propoxy, butoxy or isocyanate groups and chlorosilanes are particularly suitable.
• n and m independently of one another are an integer from 0 to 20 and together result in a maximum of 30 and R is a straight-chain, branched, saturated or unsaturated (optionally containing heteroatoms) C 1 -C 8 -alkyl radical.
• Preferred alkyl radicals are methyl, ethyl and propyl radicals, and their amino derivatives.
• silanes which have functional groups which comprise heteroatoms or heteroatoms and which increase or mediate the water solubility of the silane.
• the heteroatoms and / or functional groups are built into the backbone of the alkyl carbon chain and / or the fluoroalkyl carbon chain and / or are present as a substituent thereon.
• Aminoalkyl groups and / or amino-fluoroalkyl groups are particularly preferred according to the invention.
• the fluorinated blocks are 1-10, in particular 1-8, and for m 0-10, in particular 0-8.
• the weight ratio of hydrophobic substance to gel network is preferably se 0.01: 1 to 1: 1, with ratios between 0.05: 1 and 0.2: 1 being preferred.
• the mixture of gel and hydrophobic substance according to the invention is applied by means of customary coating methods, spraying and dip coating being preferred.
• the thickness of the coating can be controlled by controlling the viscosity and the rate at which the object to be coated is pulled out of the dipping solution.
• the coating mixture therefore also contains viscosity modifiers such as PVP, PVA and PEO.
• Layer thicknesses which can preferably be produced according to the invention are between 0.5 nm and 1 ⁇ m, layer thicknesses of ⁇ 200 nm being preferred.
• the layer is preferably dried at room temperature for at least 1 minute, preferably at least 3 minutes, and then cured at elevated temperature, any substances added, such as the viscosity modifiers, being pyrolyzed or burned.
• the drying time depends on the layer thickness generated, the actual temperature and the vapor pressure of the solvent and is preferably at least 1 minute and in particular at least 3 minutes. Usual drying times are 4 - 6 minutes.
• the applied layer is preferably sintered or hardened at temperatures of 150 ° C. to 400 ° C., preferably at 250 ° C. to 380 ° C.
• the duration of the curing is usually a maximum of 1 hour, with a maximum of 45 minutes and in particular a maximum of 30 minutes being preferred.
• the degree of hydrolysis it is possible to set the viscosity of the coating solution, in particular the immersion solution, exactly to a drawable value. In this way, with a known viscosity and a known drawing speed, the layer thickness produced in each case can be accurately be produced producible.
• a change in the viscosity when using the coating or immersion solution can be adjusted to the desired value in a simple manner by dilution with solvents, for example ethanol or by metering in further sol-gel solution capable of hydrolysis.
• the method according to the invention it is also possible to adapt the refractive index of the coating to the carrier material. This is possible, for example, by mixing different metal oxides.
• the method according to the invention is also particularly suitable for producing interference coatings, such as, for example, for anti-reflective treatment.
• the permanently hydrophobic layer is provided with a surface microstructure by means of suitable measures before, during or after the thermal curing, as a result of which the hydrophobic properties of the coating are strengthened and its cleaning is facilitated or the layer is given an anti-reflective effect or is enhanced ,
• Such measures can be created by embedding particles or embossing.
• surface microstructures can be achieved which, for example, have knobs which restrict contact of contaminating parts with the surface coated according to the invention to a few points of contact, as is the case, for example, with the so-called lotus effect. In this way, the desired cleaning effect is further increased.
• any materials that survive the previously described sintering temperature using the method according to the invention.
• These include in particular metals, plastics, inorganic minerals and stones such as marble, granite, fired clays.
• glass and glass ceramics by means of the method according to the invention.
• Preferred glasses are borosilicate glasses, soda-lime glasses and optical glasses.
• the method according to the invention is particularly suitable for the production of easily cleanable flat and, in particular, float glasses, of curved glasses, optical lenses, glass tubes, TV and PC screens and cover panes therefor, of glass ceramic products, vehicle glazing, enamelled and / or ceramic products.
• Preferred flat glasses are, for example, window glass, mirror glasses, shower cubicle glasses, glass shelves, cover glasses for solar collectors, sight glasses, instrument glasses, glass keyboards, touch screen panels, display cover glasses, for example for mobile telephones and laptops, glasses for cookers, such as oven panes, glass baking dishes or / and glass baking molds, lamp cover glasses, as well as glasses for refrigerators and furniture.
• Domed glasses are, for example, headlight glasses, lamp cover glasses, watch glasses and / or sanitary glasses.
• Glass lenses are, for example, glasses, eyepieces and objective glasses in optical devices.
• Glass tubes are, for example, solar collector tubes and sewage pipes.
• Vehicle glazings are, for example, windows and instrument cover glasses for motor vehicles, rail vehicles such as trains etc., ships and planes.
• Enamelled products include baking trays, saucepans and sanitary objects such as wash basins, urinals, bathtubs and toilet bowls. Ceramic products are, for example, tiles, roof tiles and the sanitary objects already mentioned.
• the method according to the invention is also suitable for coating objects in the household, such as drinking glasses, glass cookware and cooktops made of glass ceramic, as are available, for example, under the trade name CERAN.
• the method according to the invention has also proven to be suitable for coating enamelled cookware, such as pans and pots.
• the method according to the invention can also be used to generate interference-optical layer packets, such as reflections.
• Such anti-reflective coatings according to the invention are preferably produced as the outermost layer adjacent to the environment or air.
• the coating was applied by means of a single immersion process. It was then dried for five minutes at room temperature and at 250 ° C for burned in for a maximum of 30 minutes, causing the silica gel to harden.
• a cleaned, 10 x 20 cm large and 2 mm thick plate made of borosilicate glass was immersed at room temperature in the SiO 2 immersion solution previously described in Example 1 and pulled out of the solution at a rate of 20 cm / min.
• the coated layer was then dried for 5 minutes at room temperature and then baked in an oven at 250 ° C. (Table 1, layer 1) or at 300 ° C. (Table 1, layer 2) for 20 minutes. After baking, the layer according to the invention had a thickness of approximately 120 nm.
• the hydrophobization was assessed by determining the contact angle with water. It was carried out with a contact angle measuring device "G10" from KRÜSS, Hamburg. For example, freshly cleaned glass surfaces show a contact angle of ⁇ 20 degrees, stored glass surfaces about 60 degrees and freshly hydrophobicized surfaces ⁇ 100 degrees.
• a value of 110 degrees was measured in this way at room temperature.
• the contact angle was still 102 degrees, after 1000 load cycles cycles 103 degrees and after 2000 load cycles still 100 degrees with a measuring accuracy of ⁇ 3 degrees.
• Example 3 (comparative example) - Hydrophobization by using a fluoroalkylsilane
• Example 4 (comparative example) - Hydrophobization by using a silicone oil

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Citations (8)

• 2002
  • 2002-05-17 EP EP02747157A patent/EP1397319A1/de not_active Withdrawn
  • 2002-05-17 WO PCT/DE2002/001778 patent/WO2002094729A1/de active Application Filing
  • 2002-05-17 JP JP2002591406A patent/JP2004529057A/ja active Pending
  • 2002-05-17 DE DE10292191T patent/DE10292191D2/de not_active Expired - Fee Related
  • 2002-05-17 CA CA002447414A patent/CA2447414A1/en not_active Abandoned
  • 2002-05-17 CN CNA028101367A patent/CN1509258A/zh active Pending

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