EP2928838A1 - Glass panel having at least one protective layer comprising tin-zinc oxide - Google Patents

Glass panel having at least one protective layer comprising tin-zinc oxide

Info

Publication number
EP2928838A1
EP2928838A1 EP13791814.0A EP13791814A EP2928838A1 EP 2928838 A1 EP2928838 A1 EP 2928838A1 EP 13791814 A EP13791814 A EP 13791814A EP 2928838 A1 EP2928838 A1 EP 2928838A1
Authority
EP
European Patent Office
Prior art keywords
protective layer
glass
disc
weight
tin
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP13791814.0A
Other languages
German (de)
French (fr)
Inventor
Anais RENIER
Philippe Letocart
Andreas Kasper
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Glass France SAS
Original Assignee
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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 Saint Gobain Glass France SAS, Compagnie de Saint Gobain SA filed Critical Saint Gobain Glass France SAS
Priority to EP13791814.0A priority Critical patent/EP2928838A1/en
Publication of EP2928838A1 publication Critical patent/EP2928838A1/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • C03C17/2453—Coating containing SnO2
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/069—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of intumescent material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • B32B17/10201—Dielectric coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/1077—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
    • 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
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/211—SnO2
    • 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
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/216—ZnO
    • 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
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/154—Deposition methods from the vapour phase by sputtering
    • C03C2218/155—Deposition methods from the vapour phase by sputtering by reactive sputtering

Definitions

  • the invention relates to a pane, in particular a glass pane, with a protective layer for reducing the glass corrosion of the pane during aging and storage. Furthermore, the invention relates to a method for producing such a disc and its use.
  • Float methods are known, for example, from FR 1 378 839 A.
  • a doughy-liquid glass melt is continuously passed from one side to an elongate bath of liquid tin in a continuous process.
  • the glass melt floats on the tin bath and a uniform glass film spreads.
  • the surface tension of the liquid glass forms a very smooth glass surface.
  • the glass melt is cooled down and solidified.
  • Flat glass may corrode under adverse environmental conditions or storage conditions, and especially in the presence of water or moisture.
  • the glass corrosion can be so strong that it is even visible to the naked eye. But even an invisible corrosion layer changes the properties of the glass surface, so that some technologies, such as vacuum coating, are no longer readily possible. Glass corrosion often leads to complaints, as the affected glass has to be replaced or subsequently polished at great expense.
  • alumina Al 2 O 3
  • the object of the present invention is now to provide a disk having improved resistance to glass corrosion and in particular reduced haze and irrigation during storage and Aging.
  • a disc according to the invention comprises
  • At least one glass with a first side and a second side and
  • At least one protective layer which is arranged flat on the first side and / or the second side of the glass sheet and
  • the protective layer contains tin-zinc oxide.
  • the glass pane according to the invention is advantageously a flat glass pane which is produced by a float process or a drawing glass process.
  • the present invention is based on the following finding by the inventors:
  • melt accelerators so-called network converters
  • the network converters are usually the oxides of sodium, potassium, magnesium and calcium.
  • the disadvantage of these additives is that they make the produced glass susceptible to corrosion.
  • the alkali oxides and in particular sodium oxide and potassium oxide diffuse out of the glass at room temperature and can react with the ambient humidity. They form a lye that attacks the glass surface by increasingly dissolving the silica network.
  • a gel layer forms.
  • crystalline precipitates also form with the gases of the ambient air, in particular C0 2 and S0 2, and in particular carbonate crystals or sulfate crystals.
  • the remaining glass surface is porous and has an iridescent effect due to its different refractive index. With aging, this effect can increase and the glass surface become increasingly cloudy and iridescent.
  • the inventors have now recognized that a protective layer according to the invention avoids or significantly reduces this effect.
  • the protective layer of the invention thus has the particular advantage that it significantly increases the shelf life of the disc and the stored disc is suitable for downstream process steps, such as a vacuum coating. Furthermore, the life of the disc is increased, so that replacement of the disc or polishing of the glass surface can be avoided or delayed. The review is preserved and is neither clouded nor falsified in their color.
  • the protective layer pane according to the invention is particularly advantageous when the pane is used in a humid, corrosive environment and, in particular, in a marine environment and in the presence of salt water.
  • the disc according to the invention contains a protective layer of tin-zinc oxide.
  • Slices with protective coatings containing tin-zinc oxide showed a particularly low glass corrosion and a particularly low turbidity during storage and aging.
  • the protective layer contains a tin-zinc oxide with a ratio of zinc: tin of 5% by weight: 95 wt .-% to 95 wt .-%: 5 wt .-% and preferably of 15 wt %: 85 wt% to 70 wt%: 30 wt%.
  • the protective layer consists only of tin-zinc oxide and production-related admixtures of other metals. Protective layers of tin-zinc oxide with such mixing ratios and compositions are particularly resistant and show a particularly low haze during aging.
  • the protective layer contains Sn x Zn y O z with 0 ⁇ z ⁇ (y + 2x) and preferably 0.7 * (y + 2x) ⁇ z ⁇ (y + 2x), and particularly preferably 0, 9 * (y + 2x) ⁇ z ⁇ (y + 2x).
  • Protective layers of tin-zinc oxide with such mixing ratios are particularly resistant and show very little corrosion.
  • Protective layers of tin-zinc oxide with such Mixing ratios are particularly stable and show a particularly low corrosion and a particularly low turbidity during storage and aging.
  • the protective layer according to the invention contains dopants, for example of antimony, fluorine, silver, ruthenium, palladium, aluminum and tantalum.
  • the proportion of doping in the metallic portion of the protective layer in weight percent (wt .-%) is preferably from 0 wt .-% to 10 wt .-% and particularly preferably from 1 wt .-% to 5 wt .-%. Washers with protective layers, which have such a doping, showed a particularly low corrosion.
  • the protective layer consists of tin-zinc oxide and optionally of a doping metal and only from production-related admixtures of other substances.
  • Protective layers of tin-zinc oxide with such mixing ratios are particularly resistant and show particularly low turbidity during storage and aging.
  • the deposition of the tin-zinc oxide takes place, for example, with the addition of oxygen as the reaction gas during the sputtering of a tin-zinc target.
  • the layer thickness d of the protective layer is from 2 nm to 500 nm, preferably from 3 nm to 50 nm and particularly preferably from 5 nm to 30 nm.
  • Discs of the invention with protective layer having these layer thicknesses show particularly low cloudiness during the Storage and aging.
  • the glass pane according to the invention contains a flat glass pane, which is produced in a float process and is referred to below as float glass pane.
  • the side of the float glass pane which floats on the tin bath during manufacture is referred to as the tin bath side.
  • the Zinnbadseite opposite side of the float glass is referred to as the atmosphere side.
  • the glass pane is a float glass pane and the protective layer is arranged on the atmosphere side and / or the tin bath side and preferably only on the tin bath side.
  • the tin bath side of a float glass pane becomes particularly turbid in the case of glass corrosion, so that the protective layer according to the invention particularly effectively avoids haze.
  • the glass pane contains a flat glass pane, which is produced in a drawing process.
  • the glass sheet according to the invention preferably contains soda-lime glass.
  • the glass pane according to the invention preferably contains a network converter which reduces the process temperature during the production of the glass pane.
  • network transducers are preferably alkaline and contain in particular sodium oxide, potassium oxide, magnesium oxide or calcium oxide or mixtures thereof.
  • the glass sheet according to the invention preferably contains less than 0.2% by weight of aluminum oxide (Al 2 O 3 ).
  • Aluminum oxide Al 2 O 3
  • Such glass panes without a specific addition of aluminum oxide are particularly susceptible to corrosion in a moist environment and are particularly well protected by the protective layer according to the invention.
  • the glass sheet according to the invention contains very little iron oxide (Fe 2 0 3 ).
  • the glass sheet according to the invention preferably contains less than 0.02 wt .-% iron oxide (Fe 2 0 3 ).
  • This low-iron glass naturally has a particularly high light transmission and is mainly used as a cover glass for photovoltaic elements, but also elsewhere in architecture. It is melted from particularly pure and especially low-iron raw materials and is therefore higher quality than normal float glass.
  • iron-poor glass is particularly susceptible to corrosion and is particularly well protected by the protective layer according to the invention.
  • the glass sheet is advantageously thermally toughened or partially prestressed.
  • the thermally partially prestressed or tempered glass sheet preferably has a preload of 30 MPa to 200 MPa and more preferably of 70 MPa to 200 MPa.
  • the thickness of the glass can vary widely and can be adapted perfectly to the requirements of the individual case. It is preferable to use disks with the standard thicknesses of 1.0 mm to 25 mm and preferably of 2 mm to 12 mm.
  • the size of the disc can vary widely and depends on the size of the use according to the invention.
  • the glass sheet may have any three-dimensional shape.
  • the three-dimensional shape has no shadow zones, so that it can be coated, for example, by sputtering.
  • the disc is planar or slightly or strongly bent in one direction or in several directions of the space.
  • the glass pane can be colorless or colored.
  • the pane according to the invention can consist of a composite of two or more individual glass panes, which are each connected to one another via at least one intermediate layer.
  • the intermediate layer preferably contains a thermoplastic such as polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), polyurethane (PU), polyethylene terephthalate (PET) or multiple layers thereof, preferably with thicknesses of 0.3 mm to 0.9 mm.
  • PVB polyvinyl butyral
  • EVA ethylene vinyl acetate
  • PU polyurethane
  • PET polyethylene terephthalate
  • the pane according to the invention can also be an insulating glass pane in which one or more individual glass panes are connected via evacuated or gas-filled intermediate spaces.
  • the pane according to the invention may also be a fire-resistant glazing, in which one or more individual glass panes are connected in a planar manner via fire protection layers.
  • fire protection layers preferably contain an intumescent, alkaline hydrogel, or hydrous alkali polysilicate, which foams when exposed to heat
  • the protective layer according to the invention is then advantageously arranged on at least one of the outer surfaces of the laminated glass pane, the insulating glass pane or the fire-resistant glazing.
  • a pane according to the invention is remote from the glass pane and the protective layer or on the glass Surface of the protective layer at least one further layer arranged.
  • the further layer can, for example, influence the optical properties of the pane.
  • Such a further layer for example, increases the transmission through the pane, reduces reflections or gives a color to the transmitted light.
  • the further layer may also be a low-E layer with a low emissivity for thermal radiation.
  • the pane according to the invention is advantageously permeable to electromagnetic radiation, preferably electromagnetic radiation of a wavelength of 300 to 1,300 nm, and in particular to visible light.
  • Period means that the total transmission through the disk has a transmission of greater than 50%, preferably greater than 70%, and most preferably greater than 90%.
  • the invention comprises a method for producing a disk, wherein at least: a. a glass sheet is provided with a first side and a second side and
  • a protective layer is applied to the first side and / or to the second side, the protective layer containing a tin-zinc oxide.
  • the application of the protective layer in process step (b) can be carried out by methods known per se, preferably by magnetic field-assisted sputtering. This is particularly advantageous in terms of a simple, fast, inexpensive and uniform coating of the glass.
  • a method for producing tin-zinc oxide layers by reactive cathode sputtering is known, for example, from DE 198 48 751 C1.
  • the tin-zinc oxide is preferably deposited with a target which comprises from 5% by weight to 95% by weight of zinc, from 5% by weight to 95% by weight of tin and from 0% by weight to 10% by weight. contains -% of a doping metal such as antimony and production-related admixtures.
  • the target particularly preferably contains from 15% by weight to 70% by weight of zinc, from 30% by weight to 85% by weight of tin and from 0% by weight to 5% by weight of antimony, as well as by other admixtures Elements.
  • the deposition of the tin-zinc oxide takes place, for example, with the addition of oxygen as the reaction gas during cathode sputtering.
  • the protective layer may be deposited by vapor deposition, chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), sol-gel or wet chemical methods.
  • the glass sheet is thermally toughened or partially prestressed before method step (a) or between method steps (a) and (b).
  • a glass sheet of float glass having an atmosphere side and a tin bath side is provided and
  • a protective layer is applied to the atmosphere side and / or the tin bath side, the protective layer containing a tin-zinc oxide.
  • the protective layer is applied only to the tin bath side of the float glass pane.
  • the invention further comprises the use of a protective layer according to the invention on a glass pane to prevent glass corrosion during storage and / or when using the pane under harsh, glass-damaging conditions, preferably in moist, moist warm or marine environment.
  • the invention further comprises the use of the pane according to the invention as part of an external facade or internal facade of a window in a building or in a vehicle on land, water or in the air or as a built-in part in furniture and appliances.
  • Particularly preferred is the use of the disc according to the invention under moist, moist and / or marine conditions, in particular as glazing near the coast or on the water, on boats or ships, in swimming pools, saunas or greenhouses.
  • the protective layer When using the protective layer according to the invention to prevent glass corrosion during storage, the protective layer is advantageously arranged on both sides of the glass pane.
  • the protective layer When using the protective layer according to the invention to prevent glass corrosion during aging and in particular under rough and glass-damaging environmental conditions such as humidity and moisture, the protective layer is advantageously arranged at least on the damaging environmental conditions facing sides of the glass sheet.
  • FIG. 1 shows a schematic cross-sectional view of a pane according to the invention
  • FIG. 2 shows a schematic cross-sectional view of an alternative embodiment of a pane according to the invention
  • Figure 3 is a schematic cross-sectional view of an alternative embodiment of a disc according to the invention.
  • FIG. 4 shows a flow chart of an exemplary embodiment of the method according to the invention.
  • FIG. 1 shows a schematic representation of a disc 10 according to the invention in a cross section.
  • the pane 10 comprises a glass pane 1 with a first side I and a second side II.
  • the glass pane 1 is, for example, a flat glass pane and in particular a float glass pane made of soda-lime glass.
  • the first side I is, for example, the atmosphere side of the float glass pane and the second side II is the tin bath side.
  • the glass sheet 1 has, for example, a thickness b of 2 mm and dimensions of 2 m ⁇ 3 m. It is understood that the glass sheet 1 may also have other, adapted to the particular purpose thicknesses and dimensions.
  • a protective layer 2 is arranged flat.
  • the protective layer 2 extends, for example, completely over the entire second side II of the glass pane 1. This can ensure that the surface of the second side II of the glass pane 1 is protected against corrosion, turbidity and Irleiter. It is understood that the protective layer 2 can also be arranged on the surface of the first side I.
  • the protective layer 2 is preferably arranged at least on the side of the glass pane 1 which, in use, is exposed to harsh and glass-damaging conditions such as moisture and moisture. This is, for example, the outside of a window of a building or a vehicle and in particular the living space or vehicle interior facing away from the glazing.
  • the protective layer 2 contains, for example, antimony-doped tin-zinc oxide and was deposited by sputtering.
  • the target for depositing the protective layer 2 contained, for example, 68% by weight of tin, 30% by weight of zinc and 2% by weight of antimony. The deposition took place with the addition of oxygen as the reaction gas during cathode sputtering.
  • the thickness d of the protective layer 2 is, for example, 25 nm.
  • FIG. 2 shows a schematic cross-sectional illustration of a further exemplary embodiment of a pane 10 according to the invention.
  • the pane 10 according to the invention contains a glass pane 1 with a protective layer 2 on the second side II, as described in FIG. Furthermore, a further protective layer 2 is arranged on the first side I of the glass pane 1.
  • the further protective layer 2 has, for example, the same texture as the protective layer 2 on the second side II.
  • FIG. 3 shows a schematic cross-sectional illustration of a further exemplary embodiment of a pane 10 according to the invention.
  • the pane 10 according to the invention contains a glass pane 1 and a protective layer 2 on the second side II, as described in FIG. Furthermore, a further functional layer 3 is arranged between the second side II and the protective layer 2.
  • the further layer 3 is, for example, a layer with low emissivity for thermal radiation (low-E layer).
  • FIG. 4 shows a flow chart of an exemplary embodiment of the method according to the invention for producing a pane 10 according to FIG. 1.
  • Table 1 shows a study of the corrosion resistance of a disc 10 according to the invention according to Example 1 in comparison with two comparative examples 1A, 1B according to the prior art.
  • Comparative Example 1A according to the prior art consists of a glass plate 1 made of soda-lime glass with a content of Al 2 0 3 of less than 0.2 wt .-%. On the glass sheet 1, no protective layer 2 according to the invention is arranged.
  • the corrosion resistance of glass sheets 1 according to Comparative Example 1A is poor and a plurality of glass sheets 1 show clouding on aging and especially on contact with moisture or water.
  • Comparative Example 1 B according to the prior art consists of a glass plate 1 made of soda-lime glass with a content of Al 2 0 3 of 0.56 wt .-%. On the glass sheet 1, no protective layer 2 according to the invention is arranged. The corrosion resistance of the glass sheet 1 of Comparative Example 1 B is better than Comparative Example 1A. Nevertheless, some of the glass panes 1 according to Comparative Example 1 B exhibit turbidity on aging and in particular on contact with moisture or water.
  • Inventive discs 10 according to Example 1 consist of a glass plate 1 made of soda lime glass with a content of Al 2 0 3 of less than 0.2 wt .-%. Both on the first side I and on the second side II of the glass sheet 1, a protective layer 2 according to the invention is arranged from a 25 nm thick layer of tin-zinc oxide. The ratio of tin: zinc in the tin-zinc oxide layer is 68% by weight: 30% by weight. The corrosion resistance of the glass sheet 1 according to Example 1 is very good. There is little or no turbidity on aging or contact with moisture or water. Discs 10 according to the invention with protective layer 2 according to Example 1 exhibit markedly improved corrosion resistance in comparison with glass panes 1 according to the prior art according to Comparative Example 1A or Comparative Example 1B.
  • Table 2 shows a study of the corrosion resistance of discs 10 according to the invention according to Example 1 in comparison with two comparative examples 1A, 1B according to the prior art.
  • Comparative Example 2 according to the prior art consists of a glass pane 1 of low-iron glass of 0.015% iron oxide. On the glass sheet 1, no protective layer 2 according to the invention is arranged. The corrosion resistance of the glass pane 1 according to Comparative Example 2 is very poor and shows turbidity on aging and in particular on contact with moisture or water.
  • Inventive discs 10 according to Example 2 consist of a glass pane 1 of low-iron glass, wherein both on the first side I and on the second side II of the glass pane 1, a protective layer 2 according to the invention is arranged.
  • the protective layer 2 consists of a 25 nm thick layer of tin-zinc oxide with a ratio of tin: zinc of 68 wt .-%: 30 wt .-%.
  • the corrosion resistance of the glass sheet 1 according to Example 2 is very good. There is little or no turbidity on aging or contact with moisture or water.
  • Protective layer further layer first side of the pane, second side of the atmosphere, side of the tin bath, thickness of the glass pane 1 Thickness of the protective layer 2

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

The invention relates to a panel (10), comprising: at least one glass panel (1) having a first side (I) and a second side (II) and at least one protective layer (2) that is arranged on the first side (I) and/or the second side (II) in a planar manner, wherein the protective layer (2) comprises tin-zinc oxide.

Description

GLASSCHEIBE MIT MINDESTENS EINER SCHUTZSCHICHT, DIE ZINN-ZINKOXID ENTHÄLT  GLASS WASH WITH AT LEAST ONE PROTECTIVE LAYER CONTAINING TIN ZINC OXIDE
Die Erfindung betrifft eine Scheibe, insbesondere eine Glasscheibe, mit einer Schutzschicht zur Verminderung der Glaskorrosion der Scheibe bei Alterung und Lagerung. Des Weiteren betrifft die Erfindung ein Verfahren zur Herstellung einer solchen Scheibe und deren Verwendung. The invention relates to a pane, in particular a glass pane, with a protective layer for reducing the glass corrosion of the pane during aging and storage. Furthermore, the invention relates to a method for producing such a disc and its use.
Die technische Produktion von Flachglas erfolgt üblicherweise über Floatverfahren oder Ziehglas-Verfahren. Floatverfahren sind beispielsweise aus FR 1 378 839 A bekannt. Bei der Floatglasherstellung wird in einem kontinuierlichen Prozess eine teigig-flüssige Glasschmelze fortlaufend von einer Seite auf ein längliches Bad aus flüssigem Zinn geleitet. Die Glasschmelze schwimmt (engl, to float) auf dem Zinnbad und es breitet sich ein gleichmäßiger Glasfilm aus. Durch die Oberflächenspannung des flüssigen Glases bildet sich eine sehr glatte Glasoberfläche. Im Zinnbad wird die Glasschmelze heruntergekühlt und erstarrt. The technical production of flat glass is usually carried out by float method or drawing glass method. Float methods are known, for example, from FR 1 378 839 A. In float glass production, a doughy-liquid glass melt is continuously passed from one side to an elongate bath of liquid tin in a continuous process. The glass melt floats on the tin bath and a uniform glass film spreads. The surface tension of the liquid glass forms a very smooth glass surface. In the tin bath, the glass melt is cooled down and solidified.
Flachglas kann bei ungünstigen Umgebungsbedingungen oder Lagerungsbedingungen und insbesondere in Anwesenheit von Wasser oder Feuchtigkeit korrodieren. Die Glaskorrosion kann dabei so stark sein, dass sie sogar mit bloßem Auge sichtbar ist. Aber auch eine noch unsichtbare Korrosionsschicht verändert die Eigenschaften der Glasoberfläche, so dass manche Technologien, beispielsweise die Vakuumbeschichtung, nicht mehr ohne weiteres möglich sind. Glaskorrosion führt häufig zu Reklamationen, da das betroffene Glas ausgewechselt oder mit hohem Aufwand nachträglich poliert werden muss. Flat glass may corrode under adverse environmental conditions or storage conditions, and especially in the presence of water or moisture. The glass corrosion can be so strong that it is even visible to the naked eye. But even an invisible corrosion layer changes the properties of the glass surface, so that some technologies, such as vacuum coating, are no longer readily possible. Glass corrosion often leads to complaints, as the affected glass has to be replaced or subsequently polished at great expense.
Um die Korrosionsbeständigkeit eines solchen technischen Glases zu verbessern, kann dem Glas Aluminiumoxid (Al203) zugesetzt werden, wie aus der WO 98/40320 A1 bekannt ist. Ein Al203-Gehalt von ca. 0,5 Gew.-% bis 1 ,5 Gew.-% hat bereits die gewünschte korrosionshemmende Wirkung. Glas, dem kein Al203 zugesetzt wurde, ist deutlich weniger korrosionsresistent. In letzterem Fall kann das Glas geringe Mengen von Al203 aus Verunreinigungen der Rohstoffe enthalten. Die AI203-Konzentration beträgt dann üblicherweise weniger als 0,2 Gew.-%. In order to improve the corrosion resistance of such a technical glass, alumina (Al 2 O 3 ) may be added to the glass, as known from WO 98/40320 A1. An Al 2 0 3 content of about 0.5 wt .-% to 1, 5 wt .-% already has the desired corrosion-inhibiting effect. Glass, to which no Al 2 O 3 was added, is much less resistant to corrosion. In the latter case, the glass may contain small amounts of Al 2 0 3 from impurities in the raw materials. The Al 2 O 3 concentration is then usually less than 0.2 wt .-%.
Die Aufgabe der vorliegenden Erfindung besteht nunmehr darin, eine Scheibe bereitzustellen, die eine verbesserte Beständigkeit gegen Glaskorrosion und insbesondere eine verringerte Trübung und Irisierung während der Lagerung und Alterung aufweist. Diese und weitere Aufgaben werden nach dem Vorschlag der Erfindung durch eine Scheibe mit den Merkmalen der unabhängigen Patentansprüche gelöst. Vorteilhafte Ausgestaltungen der Erfindung sind durch die Merkmale der Unteransprüche angegeben. The object of the present invention is now to provide a disk having improved resistance to glass corrosion and in particular reduced haze and irrigation during storage and Aging. These and other objects are achieved according to the proposal of the invention by a disc having the features of the independent claims. Advantageous embodiments of the invention are indicated by the features of the subclaims.
Ein Verfahren zur Herstellung einer Scheibe sowie die Verwendung gehen aus weiteren unabhängigen Patentansprüchen hervor. A process for the production of a disc and the use are evident from further independent patent claims.
Eine erfindungsgemäße Scheibe umfasst A disc according to the invention comprises
- mindestens eine Glasscheibe mit einer ersten Seite und einer zweiten Seite und - At least one glass with a first side and a second side and
- mindestens eine Schutzschicht, die auf der ersten Seite und/oder der zweiten Seite der Glasscheibe flächig angeordnet ist und - At least one protective layer which is arranged flat on the first side and / or the second side of the glass sheet and
wobei die Schutzschicht Zinn-Zinkoxid enthält. wherein the protective layer contains tin-zinc oxide.
Die erfindungsgemäße Glasscheibe ist vorteilhafterweise eine Flachglasscheibe, die durch Float-Verfahren oder Ziehglas-Verfahren hergestellt wird. The glass pane according to the invention is advantageously a flat glass pane which is produced by a float process or a drawing glass process.
Die vorliegende Erfindung beruht auf der folgenden Erkenntnis der Erfinder: Die technische Produktion von Flachglas setzt voraus, dass bei der Schmelze Schmelzbeschleuniger, sogenannte Netzwerkwandler, zugesetzt werden. Diese geben dem Glas die erforderlichen Eigenschaften, wie Schmelzpunkt, Erweichungspunkt und Formbarkeitsintervall um das Flachglas zu formen. Als Netzwerkwandler fungieren meist die Oxide von Natrium, Kalium, Magnesium und Kalzium. The present invention is based on the following finding by the inventors: The technical production of flat glass requires that melt accelerators, so-called network converters, be added to the melt. These give the glass the required properties, such as melting point, softening point and moldability interval to form the flat glass. The network converters are usually the oxides of sodium, potassium, magnesium and calcium.
Der Nachteil dieser Zusätze ist, dass sie das produzierte Glas korrosionsanfällig machen. Die Alkali-Oxide und insbesondere Natriumoxid und Kaliumoxid diffundieren schon bei Raumtemperatur aus dem Glas heraus und können mit der Umgebungsfeuchte reagieren. Dabei bilden sie eine Lauge, die die Glasoberfläche angreift, indem sie das Kieselsäurenetzwerk zunehmend auflöst. Zunächst bildet sich eine Gelschicht. An manchen prädisponierten Stellen bilden sich auch kristalline Ausscheidungen mit den Gasen der Umgebungsluft, vor allem aus C02 und S02 und insbesondere Karbonatkristalle beziehungsweise Sulfatkristalle. The disadvantage of these additives is that they make the produced glass susceptible to corrosion. The alkali oxides and in particular sodium oxide and potassium oxide diffuse out of the glass at room temperature and can react with the ambient humidity. They form a lye that attacks the glass surface by increasingly dissolving the silica network. First, a gel layer forms. In some predisposed areas, crystalline precipitates also form with the gases of the ambient air, in particular C0 2 and S0 2, and in particular carbonate crystals or sulfate crystals.
Die verbleibende Glasoberfläche ist porös und hat auf Grund ihrer unterschiedlichen Brechzahl eine irisierende Wirkung. Bei Alterung kann dieser Effekt zunehmen und die Glasoberfläche zunehmend trübe und irisierend werden. Die Erfinder haben nun erkannt, dass eine erfindungsgemäße Schutzschicht diesen Effekt vermeidet oder deutlich vermindert. Die erfindungsgemäße Schutzschicht hat somit den besonderen Vorteil, dass sie die Lagerfähigkeit der Scheibe deutlich erhöht und die gelagerte Scheibe für nachgelagerte Prozessschritte, wie eine Vakuumbeschichtung, geeignet erhält. Des Weiteren wird die Lebensdauer der Scheibe erhöht, so dass ein Austausch der Scheibe oder ein Polieren der Glasoberfläche vermieden oder hinausgezögert werden kann. Die Durchsicht bleibt erhalten und ist weder getrübt noch in ihrer Färbung verfälscht. The remaining glass surface is porous and has an iridescent effect due to its different refractive index. With aging, this effect can increase and the glass surface become increasingly cloudy and iridescent. The inventors have now recognized that a protective layer according to the invention avoids or significantly reduces this effect. The protective layer of the invention thus has the particular advantage that it significantly increases the shelf life of the disc and the stored disc is suitable for downstream process steps, such as a vacuum coating. Furthermore, the life of the disc is increased, so that replacement of the disc or polishing of the glass surface can be avoided or delayed. The review is preserved and is neither clouded nor falsified in their color.
Die erfindungsgemäße Scheibe mit Schutzschicht ist besonders vorteilhaft, wenn die Scheibe in feuchtwarmer, korrosiver Umgebung eingesetzt wird und insbesondere in mariner Umgebung und bei Anwesenheit von Salzwasser. The protective layer pane according to the invention is particularly advantageous when the pane is used in a humid, corrosive environment and, in particular, in a marine environment and in the presence of salt water.
Die erfindungsgemäße Scheibe enthält eine Schutzschicht aus Zinn-Zinkoxid. Scheiben mit Schutzschichten, die Zinn-Zinkoxid enthalten, zeigten eine besonders geringe Glaskorrosion und eine besonders geringe Trübung bei der Lagerung und der Alterung. The disc according to the invention contains a protective layer of tin-zinc oxide. Slices with protective coatings containing tin-zinc oxide showed a particularly low glass corrosion and a particularly low turbidity during storage and aging.
In einer vorteilhaften Ausgestaltung der erfindungsgemäßen Scheibe enthält die Schutzschicht ein Zinn-Zinkoxid mit einem Verhältnis von Zink:Zinn von 5 Gew.- % : 95 Gew.-% bis 95 Gew.-% : 5 Gew.-% und bevorzugt von 15 Gew.-% : 85 Gew.-% bis 70 Gew.-% : 30 Gew.-%. In einer besonders vorteilhaften Ausgestaltung der erfindungsgemäßen Scheibe besteht die Schutzschicht nur aus Zinn-Zinkoxid sowie herstellungsbedingten Beimengungen anderer Metalle. Schutzschichten aus Zinn- Zinkoxid mit derartigen Mischungsverhältnissen und Zusammensetzungen sind besonders beständig und zeigen eine besonders geringe Trübung während der Alterung. In an advantageous embodiment of the pane according to the invention the protective layer contains a tin-zinc oxide with a ratio of zinc: tin of 5% by weight: 95 wt .-% to 95 wt .-%: 5 wt .-% and preferably of 15 wt %: 85 wt% to 70 wt%: 30 wt%. In a particularly advantageous embodiment of the disc according to the invention, the protective layer consists only of tin-zinc oxide and production-related admixtures of other metals. Protective layers of tin-zinc oxide with such mixing ratios and compositions are particularly resistant and show a particularly low haze during aging.
In einer vorteilhaften Ausgestaltung einer erfindungsgemäßen Scheibe enthält die Schutzschicht SnxZnyOz mit 0 < z < (y+2x) und bevorzugt 0,7*(y+2x) < z < (y+2x) und besonders bevorzugt 0,9*(y+2x)< z < (y+2x). Schutzschichten aus Zinn-Zinkoxid mit derartigen Mischungsverhältnissen sind besonders beständig und zeigen besonders wenig Korrosion. In einer besonders vorteilhaften Ausgestaltung der erfindungsgemäßen Scheibe enthält die Schutzschicht ZnSn03 oder Zn2Sn04 oder Gemische davon. Schutzschichten aus Zinn-Zinkoxid mit derartigen Mischungsverhältnissen sind besonders beständig und zeigen eine besonders geringe Korrosion und eine besonders geringe Trübung während der Lagerung und der Alterung. In an advantageous embodiment of a pane according to the invention, the protective layer contains Sn x Zn y O z with 0 <z <(y + 2x) and preferably 0.7 * (y + 2x) <z <(y + 2x), and particularly preferably 0, 9 * (y + 2x) <z <(y + 2x). Protective layers of tin-zinc oxide with such mixing ratios are particularly resistant and show very little corrosion. In a particularly advantageous embodiment of the pane according to the invention, the protective layer ZnSn0 3 or Zn 2 Sn0 4 or mixtures thereof. Protective layers of tin-zinc oxide with such Mixing ratios are particularly stable and show a particularly low corrosion and a particularly low turbidity during storage and aging.
In einer vorteilhaften Ausgestaltung enthält die erfindungsgemäße Schutzschicht Dotierungen, beispielsweise von Antimon, Fluor, Silber, Ruthenium, Palladium, Aluminium und Tantal. Der Anteil der Dotierung am metallischen Anteil der Schutzschicht in Gewichtsprozent (Gew.-%) beträgt bevorzugt von 0 Gew.-% bis 10 Gew.-% und besonders bevorzugt von 1 Gew.-% bis 5 Gew.-%. Scheiben mit Schutzschichten, die eine derartige Dotierung aufweisen, zeigten eine besonders geringe Korrosion. In an advantageous embodiment, the protective layer according to the invention contains dopants, for example of antimony, fluorine, silver, ruthenium, palladium, aluminum and tantalum. The proportion of doping in the metallic portion of the protective layer in weight percent (wt .-%) is preferably from 0 wt .-% to 10 wt .-% and particularly preferably from 1 wt .-% to 5 wt .-%. Washers with protective layers, which have such a doping, showed a particularly low corrosion.
In einer vorteilhaften Ausgestaltung der Scheibe besteht die Schutzschicht aus Zinn- Zinkoxid sowie gegebenenfalls aus einem Dotiermetall und lediglich aus herstellungsbedingten Beimengungen anderer Stoffe. Schutzschichten aus Zinn- Zinkoxid mit derartigen Mischungsverhältnissen sind besonders beständig und zeigen besonders geringe Trübungen während der Lagerung und Alterung. In an advantageous embodiment of the disc, the protective layer consists of tin-zinc oxide and optionally of a doping metal and only from production-related admixtures of other substances. Protective layers of tin-zinc oxide with such mixing ratios are particularly resistant and show particularly low turbidity during storage and aging.
Die Abscheidung des Zinn-Zinkoxids erfolgt beispielsweise unter Zugabe von Sauerstoff als Reaktionsgas während der Kathodenzerstäubung eines Zinn-Zink- Targets. The deposition of the tin-zinc oxide takes place, for example, with the addition of oxygen as the reaction gas during the sputtering of a tin-zinc target.
In einer vorteilhaften Ausgestaltung einer erfindungsgemäßen Schutzschicht beträgt die Schichtdicke d der Schutzschicht von 2 nm bis 500 nm, bevorzugt von 3 nm bis 50 nm und besonders bevorzugt von 5 nm bis 30 nm. Erfindungsgemäße Scheiben mit Schutzschicht mit diesen Schichtdicken zeigten besonders geringe Trübungen während der Lagerung und der Alterung. In an advantageous embodiment of a protective layer according to the invention, the layer thickness d of the protective layer is from 2 nm to 500 nm, preferably from 3 nm to 50 nm and particularly preferably from 5 nm to 30 nm. Discs of the invention with protective layer having these layer thicknesses show particularly low cloudiness during the Storage and aging.
In einer vorteilhaften Ausgestaltung enthält die erfindungsgemäße Glasscheibe eine Flachglasscheibe, die in einem Floatverfahren hergestellt wird und im Folgenden Floatglasscheibe genannt wird. In Rahmen der vorliegenden Erfindung wird die Seite der Floatglasscheibe, die bei der Herstellung auf dem Zinnbad aufschwimmt als Zinnbadseite bezeichnet. Die der Zinnbadseite gegenüberliegende Seite der Floatglasscheibe wird als Atmosphärenseite bezeichnet. In einer besonders vorteilhaften Ausgestaltung der erfindungsgemäßen Scheibe ist die Glasscheibe eine Floatglasscheibe und die Schutzschicht auf der Atmosphärenseite und/oder der Zinnbadseite und bevorzugt nur auf der Zinnbadseite angeordnet ist. Die Zinnbadseite einer Floatglasscheibe wird bei Glaskorrosion besonders schnell trübe, so dass die erfindungsgemäße Schutzschicht besonders effektiv die Trübung vermeidet. In an advantageous embodiment, the glass pane according to the invention contains a flat glass pane, which is produced in a float process and is referred to below as float glass pane. In the context of the present invention, the side of the float glass pane which floats on the tin bath during manufacture is referred to as the tin bath side. The Zinnbadseite opposite side of the float glass is referred to as the atmosphere side. In a particularly advantageous embodiment of the pane according to the invention, the glass pane is a float glass pane and the protective layer is arranged on the atmosphere side and / or the tin bath side and preferably only on the tin bath side. The tin bath side of a float glass pane becomes particularly turbid in the case of glass corrosion, so that the protective layer according to the invention particularly effectively avoids haze.
In einer alternativen Ausgestaltung der Erfindung enthält die Glasscheibe eine Flachglasscheibe, die in einem Ziehverfahren hergestellt wird. In an alternative embodiment of the invention, the glass pane contains a flat glass pane, which is produced in a drawing process.
Die erfindungsgemäße Glasscheibe enthält bevorzugt Kalk-Natron-Glas. The glass sheet according to the invention preferably contains soda-lime glass.
Die erfindungsgemäße Glasscheibe enthält bevorzugt einen Netzwerkwandler, der die Prozesstemperatur bei der Herstellung der Glasscheibe herabsetzt. Derartige Netzwerkwandler sind bevorzugt alkalisch und enthalten insbesondere Natriumoxid, Kaliumoxid, Magnesiumoxid oder Calciumoxid oder Gemische davon. The glass pane according to the invention preferably contains a network converter which reduces the process temperature during the production of the glass pane. Such network transducers are preferably alkaline and contain in particular sodium oxide, potassium oxide, magnesium oxide or calcium oxide or mixtures thereof.
Die erfindungsgemäße Glasscheibe enthält bevorzugt weniger als 0,2 Gew.-% Aluminiumoxid (Al203). Derartige Glasscheiben ohne einen gezielten Zusatz von Aluminiumoxid sind in feuchter Umgebung besonders korrosionsanfällig und werden besonders gut durch die erfindungsgemäße Schutzschicht geschützt. The glass sheet according to the invention preferably contains less than 0.2% by weight of aluminum oxide (Al 2 O 3 ). Such glass panes without a specific addition of aluminum oxide are particularly susceptible to corrosion in a moist environment and are particularly well protected by the protective layer according to the invention.
In einer alternativen Ausgestaltung enthält die erfindungsgemäße Glasscheibe besonders wenig Eisenoxid (Fe203). Die erfindungsgemäße Glasscheibe enthält bevorzugt weniger als 0,02 Gew.-% Eisenoxid (Fe203). Dieses eisenarme Glas weist naturgemäß eine besonders hohe Lichttransmission auf und wird vorwiegend als Abdeckglas für photovoltaische Elemente, aber auch anderweitig in der Architektur verwendet. Es wird aus besonders reinen und insbesondere eisenarmen Rohstoffen erschmolzen und ist daher hochwertiger als normales Floatglas. Derartiges eisenarmes Glas ist jedoch besonders korrosionsanfällig und wird besonders gut durch die erfindungsgemäße Schutzschicht geschützt. In an alternative embodiment, the glass sheet according to the invention contains very little iron oxide (Fe 2 0 3 ). The glass sheet according to the invention preferably contains less than 0.02 wt .-% iron oxide (Fe 2 0 3 ). This low-iron glass naturally has a particularly high light transmission and is mainly used as a cover glass for photovoltaic elements, but also elsewhere in architecture. It is melted from particularly pure and especially low-iron raw materials and is therefore higher quality than normal float glass. However, such iron-poor glass is particularly susceptible to corrosion and is particularly well protected by the protective layer according to the invention.
Die Glasscheibe ist vorteilhafterweise thermisch vorgespannt oder teilvorgespannt. Die thermisch teilvorgespannte oder vorgespannte Glasscheibe hat bevorzugt eine Vorspannung von 30 MPa bis 200 MPa und besonders bevorzugt von 70 MPa bis 200 MPa. Die Dicke der Glasscheibe kann breit variieren und so hervorragend den Erfordernissen des Einzelfalls angepasst werden. Vorzugsweise werden Scheiben mit den Standardstärken von 1 ,0 mm bis 25 mm und bevorzugt von 2 mm bis 12 mm verwendet. Die Größe der Scheibe kann breit variieren und richtet sich nach der Größe der erfindungsgemäßen Verwendung. The glass sheet is advantageously thermally toughened or partially prestressed. The thermally partially prestressed or tempered glass sheet preferably has a preload of 30 MPa to 200 MPa and more preferably of 70 MPa to 200 MPa. The thickness of the glass can vary widely and can be adapted perfectly to the requirements of the individual case. It is preferable to use disks with the standard thicknesses of 1.0 mm to 25 mm and preferably of 2 mm to 12 mm. The size of the disc can vary widely and depends on the size of the use according to the invention.
Die Glasscheibe kann eine beliebige dreidimensionale Form aufweisen. Vorzugsweise hat die dreidimensionale Form keine Schattenzonen, so dass sie beispielsweise durch Kathodenzerstäubung beschichtet werden kann. Bevorzugt ist die Scheibe planar oder leicht oder stark in eine Richtung oder in mehrere Richtungen des Raumes gebogen. Die Glasscheibe kann farblos oder gefärbt sein. The glass sheet may have any three-dimensional shape. Preferably, the three-dimensional shape has no shadow zones, so that it can be coated, for example, by sputtering. Preferably, the disc is planar or slightly or strongly bent in one direction or in several directions of the space. The glass pane can be colorless or colored.
Die erfindungsgemäße Scheibe kann aus einem Verbund von zwei oder mehreren einzelnen Glasscheiben bestehen, die jeweils über mindestens eine Zwischenschicht miteinander verbunden sind. Die Zwischenschicht enthält vorzugsweise einen thermoplastischen Kunststoff, wie Polyvinylbutyral (PVB), Ethylenvinylacetat (EVA), Polyurethan (PU), Polyethylenterephthalat (PET) oder mehrere Schichten davon, bevorzugt mit Dicken von 0,3 mm bis 0,9 mm. The pane according to the invention can consist of a composite of two or more individual glass panes, which are each connected to one another via at least one intermediate layer. The intermediate layer preferably contains a thermoplastic such as polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), polyurethane (PU), polyethylene terephthalate (PET) or multiple layers thereof, preferably with thicknesses of 0.3 mm to 0.9 mm.
Die erfindungsgemäße Scheibe kann auch eine Isolierglasscheibe sein, bei der eine oder mehrere einzelne Glasscheiben über evakuierte oder gasgefüllte Zwischenräume verbunden sind. The pane according to the invention can also be an insulating glass pane in which one or more individual glass panes are connected via evacuated or gas-filled intermediate spaces.
Alternativ oder in Kombination, kann die erfindungsgemäße Scheibe auch eine Brandschutzverglasung sein, bei der eine oder mehrere einzelne Glasscheiben über Brandschutzschichten flächig verbunden sind. Derartige Brandschutzschichten enthalten bevorzugt ein intumeszentes, alkalisches Hydrogel, oder wasserhaltiges Alkali-Polysilikat, das bei Hitzeeinwirkung aufschäumt Alternatively or in combination, the pane according to the invention may also be a fire-resistant glazing, in which one or more individual glass panes are connected in a planar manner via fire protection layers. Such fire protection layers preferably contain an intumescent, alkaline hydrogel, or hydrous alkali polysilicate, which foams when exposed to heat
Die erfindungsgemäße Schutzschicht ist dann vorteilhafterweise auf mindestens einer der außenliegende Oberflächen der Verbundglasscheibe, der Isolierglasscheibe oder der Brandschutzverglasung angeordnet. The protective layer according to the invention is then advantageously arranged on at least one of the outer surfaces of the laminated glass pane, the insulating glass pane or the fire-resistant glazing.
In einer vorteilhaften Ausgestaltung einer erfindungsgemäßen Scheibe ist zwischen der Glasscheibe und der Schutzschicht oder auf der der Glasscheibe abgewandten Oberfläche der Schutzschicht mindestens eine weitere Schicht angeordnet. Die weitere Schicht kann beispielsweise die optischen Eigenschaften der Scheibe beeinflussen. Eine derartige weitere Schicht erhöht beispielsweise die Transmission durch die Scheibe, mindert Reflektionen oder gibt dem transmittierten Licht eine Färbung. Die weitere Schicht kann auch eine Low-E-Schicht mit einer niedrigen Emissivität für Wärmestrahlung sein. In an advantageous embodiment of a pane according to the invention is remote from the glass pane and the protective layer or on the glass Surface of the protective layer at least one further layer arranged. The further layer can, for example, influence the optical properties of the pane. Such a further layer, for example, increases the transmission through the pane, reduces reflections or gives a color to the transmitted light. The further layer may also be a low-E layer with a low emissivity for thermal radiation.
Die erfindungsgemäße Scheibe ist vorteilhafterweise für elektromagnetische Strahlung, vorzugsweise elektromagnetische Strahlung einer Wellenlänge von 300 bis 1 .300 nm, und insbesondere für sichtbares Licht, durchlässig. „Durchlässig" bedeutet, dass die Gesamttransmission durch die Scheibe eine Transmission von mehr als 50%, bevorzugt von mehr als 70% und besonders bevorzugt von mehr als 90% aufweist. The pane according to the invention is advantageously permeable to electromagnetic radiation, preferably electromagnetic radiation of a wavelength of 300 to 1,300 nm, and in particular to visible light. "Permeable" means that the total transmission through the disk has a transmission of greater than 50%, preferably greater than 70%, and most preferably greater than 90%.
Die Erfindung umfasst ein Verfahren zur Herstellung einer Scheibe, wobei mindestens: a. eine Glasscheibe mit einer ersten Seite und einer zweiten Seite bereitgestellt wird und The invention comprises a method for producing a disk, wherein at least: a. a glass sheet is provided with a first side and a second side and
b. eine Schutzschicht auf die erste Seite und/oder auf die zweite Seite aufgebracht wird, wobei die Schutzschicht ein Zinn-Zinkoxid enthält. b. a protective layer is applied to the first side and / or to the second side, the protective layer containing a tin-zinc oxide.
Das Aufbringen der Schutzschicht in Verfahrensschritt (b) kann durch an sich bekannte Verfahren erfolgen, bevorzugt durch magnetfeldunterstützte Kathodenzerstäubung. Das ist besonders vorteilhaft im Hinblick auf eine einfache, schnelle, kostengünstige und gleichmäßige Beschichtung der Glasscheibe. The application of the protective layer in process step (b) can be carried out by methods known per se, preferably by magnetic field-assisted sputtering. This is particularly advantageous in terms of a simple, fast, inexpensive and uniform coating of the glass.
Ein Verfahren zur Herstellung von Zinn-Zinkoxid-Schichten durch reaktive Kathodenzerstäubung ist beispielsweise aus DE 198 48 751 C1 bekannt. Das Zinn- Zinkoxid wird bevorzugt mit einem Target abgeschieden, welches von 5 Gew.-% bis 95 Gew.-% Zink, von 5 Gew.-% bis 95 Gew.-% Zinn und von 0 Gew.-% bis 10 Gew.-% eines Dotiermetalls wie Antimon sowie herstellungsbedingte Beimengungen enthält. Das Target enthält besonders bevorzugt von 15 Gew.-% bis 70 Gew.-% Zink, von 30 Gew.-% bis 85 Gew.-% Zinn und von 0 Gew.-% bis 5 Gew.-% Antimon sowie herstellungsbedingte Beimengungen anderer Elemente. Die Abscheidung des Zinn- Zinkoxids erfolgt beispielsweise unter Zugabe von Sauerstoff als Reaktionsgas während der Kathodenzerstäubung. Die Schutzschicht kann alternativ durch Aufdampfen, chemische Gasphasenabscheidung (chemical vapour deposition, CVD), plasmagestützte Gasphasenabscheidung (PECVD), durch Sol-Gel-Verfahren oder durch nasschemische Verfahren aufgebracht werden. A method for producing tin-zinc oxide layers by reactive cathode sputtering is known, for example, from DE 198 48 751 C1. The tin-zinc oxide is preferably deposited with a target which comprises from 5% by weight to 95% by weight of zinc, from 5% by weight to 95% by weight of tin and from 0% by weight to 10% by weight. contains -% of a doping metal such as antimony and production-related admixtures. The target particularly preferably contains from 15% by weight to 70% by weight of zinc, from 30% by weight to 85% by weight of tin and from 0% by weight to 5% by weight of antimony, as well as by other admixtures Elements. The deposition of the tin-zinc oxide takes place, for example, with the addition of oxygen as the reaction gas during cathode sputtering. Alternatively, the protective layer may be deposited by vapor deposition, chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), sol-gel or wet chemical methods.
In einer vorteilhaften Weiterbildung des erfindungsgemäßen Verfahrens wird vor dem Verfahrensschritt (a) oder zwischen den Verfahrensschritten (a) und (b) die Glasscheibe thermisch vorgespannt oder teilvorgespannt. In an advantageous development of the method according to the invention, the glass sheet is thermally toughened or partially prestressed before method step (a) or between method steps (a) and (b).
Eine alternative Ausführungsform des erfindungsgemäßen Verfahrens zur Herstellung einer Scheibe umfasst mindestens die folgenden Schritte: An alternative embodiment of the method according to the invention for producing a pane comprises at least the following steps:
a. Eine Glasscheibe aus Floatglas mit einer Atmosphärenseite und einer Zinnbadseite wird bereitgestellt und a. A glass sheet of float glass having an atmosphere side and a tin bath side is provided and
b. eine Schutzschicht wird auf die Atmosphärenseite und/oder die Zinnbadseite aufgebracht, wobei die Schutzschicht ein Zinn-Zinkoxid enthält. b. a protective layer is applied to the atmosphere side and / or the tin bath side, the protective layer containing a tin-zinc oxide.
In einer vorteilhaften Weiterbildung des erfindungsgemäßen Verfahrens wird die Schutzschicht nur auf die Zinnbadseite der Floatglasscheibe aufgebracht. In an advantageous development of the method according to the invention, the protective layer is applied only to the tin bath side of the float glass pane.
Die Erfindung umfasst weiterhin die Verwendung einer erfindungsgemäßen Schutzschicht auf einer Glasscheibe zur Vermeidung von Glaskorrosion bei Lagerung und/oder bei Verwendung der Scheibe unter rauen, glasschädigenden Bedingungen, bevorzugt in feuchter, feuchtwarmer oder mariner Umgebung. The invention further comprises the use of a protective layer according to the invention on a glass pane to prevent glass corrosion during storage and / or when using the pane under harsh, glass-damaging conditions, preferably in moist, moist warm or marine environment.
Die Erfindung umfasst weiter die Verwendung der erfindungsgemäßen Scheibe als Teil einer Außenfassade oder Innenfassade eines Fensters in einem Gebäude oder in einem Fahrzeug zu Lande, zu Wasser oder in der Luft oder als Einbauteil in Möbeln und Geräten. Besonders bevorzugt ist die Verwendung der erfindungsgemäßen Scheibe unter feuchten, feuchtwarmen und/oder marinen Bedingungen, insbesondere als Verglasung in Küstennähe oder auf dem Wasser, auf Booten oder Schiffen, in Schwimmbädern, Saunen oder Gewächshäusern. The invention further comprises the use of the pane according to the invention as part of an external facade or internal facade of a window in a building or in a vehicle on land, water or in the air or as a built-in part in furniture and appliances. Particularly preferred is the use of the disc according to the invention under moist, moist and / or marine conditions, in particular as glazing near the coast or on the water, on boats or ships, in swimming pools, saunas or greenhouses.
Bei Verwendung der erfindungsgemäßen Schutzschicht zur Vermeidung von Glaskorrosion bei Lagerung ist die Schutzschicht vorteilhafterweise auf beiden Seiten der Glasscheibe angeordnet. Bei Verwendung der erfindungsgemäßen Schutzschicht zur Vermeidung von Glaskorrosion bei Alterung und insbesondere unter rauen und glasschädigenden Umgebungsbedingungen wie Feuchte und Nässe ist die Schutzschicht vorteilhafterweise zumindest auf der den schädigenden Umgebungsbedingungen zugewandten Seiten der Glasscheibe angeordnet. When using the protective layer according to the invention to prevent glass corrosion during storage, the protective layer is advantageously arranged on both sides of the glass pane. When using the protective layer according to the invention to prevent glass corrosion during aging and in particular under rough and glass-damaging environmental conditions such as humidity and moisture, the protective layer is advantageously arranged at least on the damaging environmental conditions facing sides of the glass sheet.
Die Erfindung wird nachfolgend anhand einer Zeichnung und eines Beispiels näher erläutert. Die Zeichnung ist nicht vollständig maßstabsgetreu. Die Erfindung wird durch die Zeichnung in keiner Weise eingeschränkt. Es zeigen: The invention will be explained in more detail with reference to a drawing and an example. The drawing is not completely true to scale. The invention is not limited by the drawing in any way. Show it:
Figur 1 eine schematische Querschnittsdarstellung einer erfindungsgemäßen Scheibe, Figur 2 eine schematische Querschnittsdarstellung eines alternativen Ausführungsbeispiels einer erfindungsgemäßen Scheibe, 1 shows a schematic cross-sectional view of a pane according to the invention, FIG. 2 shows a schematic cross-sectional view of an alternative embodiment of a pane according to the invention,
Figur 3 eine schematische Querschnittsdarstellung eines alternativen Ausführungsbeispiels einer erfindungsgemäßen Scheibe und  Figure 3 is a schematic cross-sectional view of an alternative embodiment of a disc according to the invention and
Figur 4 ein Flussdiagramm eines Ausführungsbeispiels des erfindungsgemäßen Verfahrens.  FIG. 4 shows a flow chart of an exemplary embodiment of the method according to the invention.
Figur 1 zeigt eine schematische Darstellung einer erfindungsgemäßen Scheibe 10 in einem Querschnitt. Die Scheibe 10 umfasst eine Glasscheibe 1 mit einer ersten Seite I und einer zweiten Seite II. Die Glasscheibe 1 ist beispielsweise eine Flachglasscheibe und insbesondere eine Floatglasscheibe aus Kalk-Natron-Glas. Die erste Seite I ist beispielsweise die Atmosphärenseite der Floatglasscheibe und die zweite Seite II die Zinnbadseite. Die Glasscheibe 1 hat beispielsweise eine Dicke b von 2 mm und Abmessungen von 2 m x 3 m. Es versteht sich, dass die Glasscheibe 1 auch andere, an den jeweiligen Verwendungszweck angepasste Dicken und Abmessungen haben kann. Figure 1 shows a schematic representation of a disc 10 according to the invention in a cross section. The pane 10 comprises a glass pane 1 with a first side I and a second side II. The glass pane 1 is, for example, a flat glass pane and in particular a float glass pane made of soda-lime glass. The first side I is, for example, the atmosphere side of the float glass pane and the second side II is the tin bath side. The glass sheet 1 has, for example, a thickness b of 2 mm and dimensions of 2 m × 3 m. It is understood that the glass sheet 1 may also have other, adapted to the particular purpose thicknesses and dimensions.
Auf der zweiten Seite II der Glasscheibe 1 ist flächig eine Schutzschicht 2 angeordnet. Die Schutzschicht 2 erstreckt sich beispielsweise vollständig über die gesamte zweite Seite II der Glasscheibe 1 . Dadurch kann sichergestellt werden, dass die Oberfläche der zweiten Seite II der Glasscheibe 1 vor Korrosion, Trübung und Irisierung geschützt ist. Es versteht sich, dass die Schutzschicht 2 auch auf der Oberfläche der ersten Seite I angeordnet sein kann. Die Schutzschicht 2 ist bevorzugt zumindest auf der Seite der Glasscheibe 1 angeordnet, die bei der Verwendung rauen und glasschädigenden Bedingungen wie Feuchtigkeit und Nässe ausgesetzt ist. Dies ist beispielsweise die Außenseite eines Fensters eines Gebäudes oder eines Fahrzeugs und insbesondere die Wohnraum oder Fahrzeuginnenraum abgewandte Seite der Verglasung. On the second side II of the glass pane 1 a protective layer 2 is arranged flat. The protective layer 2 extends, for example, completely over the entire second side II of the glass pane 1. This can ensure that the surface of the second side II of the glass pane 1 is protected against corrosion, turbidity and Irisierung. It is understood that the protective layer 2 can also be arranged on the surface of the first side I. The protective layer 2 is preferably arranged at least on the side of the glass pane 1 which, in use, is exposed to harsh and glass-damaging conditions such as moisture and moisture. This is, for example, the outside of a window of a building or a vehicle and in particular the living space or vehicle interior facing away from the glazing.
Die Schutzschicht 2 enthält beispielsweise antimondotiertes Zinn-Zinkoxid und wurde durch Kathodenzerstäubung abgeschieden. Das Target zur Abscheidung der Schutzschicht 2 enthielt beispielsweise 68 Gew.-% Zinn, 30 Gew.-% Zink und 2 Gew.- % Antimon. Die Abscheidung erfolgte unter Zugabe von Sauerstoff als Reaktionsgas während der Kathodenzerstäubung. Die Dicke d der Schutzschicht 2 beträgt beispielsweise 25 nm. The protective layer 2 contains, for example, antimony-doped tin-zinc oxide and was deposited by sputtering. The target for depositing the protective layer 2 contained, for example, 68% by weight of tin, 30% by weight of zinc and 2% by weight of antimony. The deposition took place with the addition of oxygen as the reaction gas during cathode sputtering. The thickness d of the protective layer 2 is, for example, 25 nm.
Figur 2 zeigt eine schematische Querschnittsdarstellung eines weiteren Ausführungsbeispiels einer erfindungsgemäßen Scheibe 10. Die erfindungsgemäße Scheibe 10 enthält eine Glasscheibe 1 mit einer Schutzschicht 2 auf der zweiten Seite II, wie sie in Figur 1 beschrieben ist. Des Weiteren ist auf der ersten Seite I der Glasscheibe 1 eine weitere Schutzschicht 2 angeordnet. Die weitere Schutzschicht 2 hat beispielsweise dieselbe Beschaffenheit, wie die Schutzschicht 2 auf der zweiten Seite II. FIG. 2 shows a schematic cross-sectional illustration of a further exemplary embodiment of a pane 10 according to the invention. The pane 10 according to the invention contains a glass pane 1 with a protective layer 2 on the second side II, as described in FIG. Furthermore, a further protective layer 2 is arranged on the first side I of the glass pane 1. The further protective layer 2 has, for example, the same texture as the protective layer 2 on the second side II.
Figur 3 zeigt eine schematische Querschnittsdarstellung eines weiteren Ausführungsbeispiels einer erfindungsgemäßen Scheibe 10. Die erfindungsgemäße Scheibe 10 enthält eine Glasscheibe 1 und eine Schutzschicht 2 auf der zweiten Seite II, wie sie in Figur 1 beschrieben ist. Des Weiteren ist zwischen der zweiten Seite II und der Schutzschicht 2 eine weitere funktionelle Schicht 3 angeordnet. Die weitere Schicht 3 ist beispielsweise eine Schicht mit niedriger Emissivität für Wärmestrahlung (Low-E- Schicht). FIG. 3 shows a schematic cross-sectional illustration of a further exemplary embodiment of a pane 10 according to the invention. The pane 10 according to the invention contains a glass pane 1 and a protective layer 2 on the second side II, as described in FIG. Furthermore, a further functional layer 3 is arranged between the second side II and the protective layer 2. The further layer 3 is, for example, a layer with low emissivity for thermal radiation (low-E layer).
Figur 4 zeigt ein Flussdiagramm eines Ausführungsbeispiels des erfindungsgemäßen Verfahrens zur Herstellung einer Scheibe 10 nach Figur 1 . FIG. 4 shows a flow chart of an exemplary embodiment of the method according to the invention for producing a pane 10 according to FIG. 1.
Tabelle 1 zeigt eine Untersuchung der Korrosionsbeständigkeit einer erfindungsgemäßen Scheibe 10 nach Beispiel 1 im Vergleich mit zwei Vergleichsbeispielen 1A, 1 B nach dem Stand der Technik. Tabelle 1 Table 1 shows a study of the corrosion resistance of a disc 10 according to the invention according to Example 1 in comparison with two comparative examples 1A, 1B according to the prior art. Table 1
Vergleichsbeispiel 1A nach dem Stand der Technik besteht aus einer Glasscheibe 1 aus Kalk-Natron-Glas mit einem Anteil an Al203 von weniger als 0,2 Gew.-%. Auf der Glasscheibe 1 ist keine erfindungsgemäße Schutzschicht 2 angeordnet. Die Korrosionsbeständigkeit von Glasscheiben 1 nach Vergleichsbeispiel 1A ist schlecht und eine Vielzahl von Glasscheiben 1 zeigen Trübungen bei Alterung und insbesondere bei Kontakt mit Feuchtigkeit oder Wasser. Comparative Example 1A according to the prior art consists of a glass plate 1 made of soda-lime glass with a content of Al 2 0 3 of less than 0.2 wt .-%. On the glass sheet 1, no protective layer 2 according to the invention is arranged. The corrosion resistance of glass sheets 1 according to Comparative Example 1A is poor and a plurality of glass sheets 1 show clouding on aging and especially on contact with moisture or water.
Vergleichsbeispiel 1 B nach dem Stand der Technik besteht aus einer Glasscheibe 1 aus Kalk-Natron-Glas mit einem Anteil an Al203 von 0,56 Gew.-%. Auf der Glasscheibe 1 ist keine erfindungsgemäße Schutzschicht 2 angeordnet. Die Korrosionsbeständigkeit der Glasscheibe 1 nach Vergleichsbeispiel 1 B ist besser als bei Vergleichsbeispiel 1A. Dennoch zeigen einige der Glasscheiben 1 nach Vergleichsbeispiel 1 B Trübungen bei Alterung und insbesondere bei Kontakt mit Feuchtigkeit oder Wasser. Comparative Example 1 B according to the prior art consists of a glass plate 1 made of soda-lime glass with a content of Al 2 0 3 of 0.56 wt .-%. On the glass sheet 1, no protective layer 2 according to the invention is arranged. The corrosion resistance of the glass sheet 1 of Comparative Example 1 B is better than Comparative Example 1A. Nevertheless, some of the glass panes 1 according to Comparative Example 1 B exhibit turbidity on aging and in particular on contact with moisture or water.
Erfindungsgemäße Scheiben 10 nach Beispiel 1 bestehen aus einer Glasscheibe 1 aus Kalk-Natron-Glas mit einem Anteil an Al203 von weniger als 0,2 Gew.-%. Sowohl auf der ersten Seite I als auch auf der zweiten Seite II der Glasscheibe 1 ist eine erfindungsgemäße Schutzschicht 2 aus einer 25 nm dicken Schicht von Zinn-Zinkoxid angeordnet. Das Verhältnis von Zinn:Zink in der Zinn-Zinkoxid-Schicht beträgt 68 Gew.-% :30 Gew.-%. Die Korrosionsbeständigkeit der Glasscheibe 1 nach Beispiel 1 ist sehr gut. Es zeigen sich keine oder nur geringe Trübungen bei Alterung oder Kontakt mit Feuchtigkeit oder Wasser. Erfindungsgemäße Scheiben 10 mit Schutzschicht 2 nach Beispiel 1 zeigen eine deutlich verbesserte Korrosionsbeständigkeit im Vergleich zu Glasscheiben 1 nach dem Stand der Technik gemäß Vergleichsbeispiels 1 A oder Vergleichsbeispiel 1 B. Inventive discs 10 according to Example 1 consist of a glass plate 1 made of soda lime glass with a content of Al 2 0 3 of less than 0.2 wt .-%. Both on the first side I and on the second side II of the glass sheet 1, a protective layer 2 according to the invention is arranged from a 25 nm thick layer of tin-zinc oxide. The ratio of tin: zinc in the tin-zinc oxide layer is 68% by weight: 30% by weight. The corrosion resistance of the glass sheet 1 according to Example 1 is very good. There is little or no turbidity on aging or contact with moisture or water. Discs 10 according to the invention with protective layer 2 according to Example 1 exhibit markedly improved corrosion resistance in comparison with glass panes 1 according to the prior art according to Comparative Example 1A or Comparative Example 1B.
Tabelle 2 zeigt eine Untersuchung der Korrosionsbeständigkeit von erfindungsgemäßen Scheiben 10 nach Beispiel 1 im Vergleich zu zwei Vergleichsbeispielen 1A,1 B nach dem Stand der Technik. Table 2 shows a study of the corrosion resistance of discs 10 according to the invention according to Example 1 in comparison with two comparative examples 1A, 1B according to the prior art.
Tabelle 2 Table 2
Vergleichsbeispiel 2 nach dem Stand der Technik besteht aus einer Glasscheibe 1 aus eisenarmem Glas von 0,015 % Eisenoxid. Auf der Glasscheibe 1 ist keine erfindungsgemäße Schutzschicht 2 angeordnet. Die Korrosionsbeständigkeit der Glasscheibe 1 nach Vergleichsbeispiel 2 ist sehr schlecht und zeigt Trübungen bei Alterung und insbesondere bei Kontakt mit Feuchtigkeit oder Wasser. Comparative Example 2 according to the prior art consists of a glass pane 1 of low-iron glass of 0.015% iron oxide. On the glass sheet 1, no protective layer 2 according to the invention is arranged. The corrosion resistance of the glass pane 1 according to Comparative Example 2 is very poor and shows turbidity on aging and in particular on contact with moisture or water.
Erfindungsgemäße Scheiben 10 nach Beispiel 2 bestehen aus einer Glasscheibe 1 aus eisenarmem Glas, wobei sowohl auf der ersten Seite I als auch auf der zweiten Seite II der Glasscheibe 1 eine erfindungsgemäße Schutzschicht 2 angeordnet ist. Die Schutzschicht 2 besteht aus einer 25 nm dicken Schicht von Zinn-Zinkoxid mit einem Verhältnis von Zinn:Zink von 68 Gew.-% :30 Gew.-%. Die Korrosionsbeständigkeit der Glasscheibe 1 nach Beispiel 2 ist sehr gut. Es zeigen sich keine oder nur geringe Trübungen bei Alterung oder Kontakt mit Feuchtigkeit oder Wasser. Inventive discs 10 according to Example 2 consist of a glass pane 1 of low-iron glass, wherein both on the first side I and on the second side II of the glass pane 1, a protective layer 2 according to the invention is arranged. The protective layer 2 consists of a 25 nm thick layer of tin-zinc oxide with a ratio of tin: zinc of 68 wt .-%: 30 wt .-%. The corrosion resistance of the glass sheet 1 according to Example 2 is very good. There is little or no turbidity on aging or contact with moisture or water.
Dieses Ergebnis war für den Fachmann unerwartet und überraschend. Bezugszeichenliste This result was unexpected and surprising to the skilled person. LIST OF REFERENCE NUMBERS
Glasscheibe pane
Schutzschicht weitere Schicht Scheibe erste Seite, Atmosphärenseite zweite Seite, Zinnbadseite Dicke der Glasscheibe 1 Dicke der Schutzschicht 2  Protective layer further layer first side of the pane, second side of the atmosphere, side of the tin bath, thickness of the glass pane 1 Thickness of the protective layer 2

Claims

Patentansprüche claims
1 . Scheibe (10), umfassend: 1 . Disc (10) comprising:
mindestens eine Glasscheibe (1 ) mit einer ersten Seite (I) und einer zweiten Seite (II) und  at least one glass pane (1) having a first side (I) and a second side (II) and
mindestens eine Schutzschicht (2), die auf der ersten Seite (I) und/oder der zweiten Seite (II) flächig angeordnet ist,  at least one protective layer (2), which is arranged flat on the first side (I) and / or the second side (II),
wobei die Schutzschicht (2) Zinn-Zinkoxid enthält.  wherein the protective layer (2) contains tin-zinc oxide.
2. Scheibe (10) nach Anspruch 1 , wobei die Schutzschicht (2) Zinn-Zinkoxid mit einem Verhältnis von Zink:Zinn von 5 Gew.-%:95 Gew.-% bis 95 Gew.-%:5 Gew.-% und bevorzugt von 15 Gew.-%:85 Gew.-% bis 70 Gew.-%:30 Gew.-% enthält. The disc (10) according to claim 1, wherein the protective layer (2) is tin-zinc oxide having a zinc: tin ratio of 5 wt%: 95 wt% to 95 wt%: 5 wt% and preferably from 15% by weight: from 85% by weight to 70% by weight: 30% by weight.
3. Scheibe (10) nach Anspruch 1 oder 2, wobei die Schutzschicht (2) aus Zinn- Zinkoxid sowie herstellungsbedingten Beimengungen besteht. 3. disc (10) according to claim 1 or 2, wherein the protective layer (2) consists of tin-zinc oxide and production-related admixtures.
4. Scheibe (10) nach einem der Ansprüche 1 bis 3, wobei die Schutzschicht SnxZnyOz mit 0 < z < (y+2x), bevorzugt 0,7*(y+2x)< < z < (y+2x) und besonders bevorzugt 0,9*(y+2x)< z < (y+2x) enthält. 4. disc (10) according to any one of claims 1 to 3, wherein the protective layer Sn x Zn y O z with 0 <z <(y + 2x), preferably 0.7 * (y + 2x) <<z <(y + 2x), and more preferably 0.9 * (y + 2x) <z <(y + 2x).
5. Scheibe (10) nach einem der Ansprüche 1 bis 4, wobei die Schutzschicht (2) eine Dicke d von 2 nm bis 500 nm, bevorzugt von 5 nm bis 50 nm und besonders bevorzugt von 15 nm bis 30 nm aufweist. 5. disc (10) according to any one of claims 1 to 4, wherein the protective layer (2) has a thickness d of 2 nm to 500 nm, preferably from 5 nm to 50 nm and more preferably from 15 nm to 30 nm.
6. Scheibe (10) nach einem der Ansprüche 1 bis 5, wobei die Glasscheibe (1 ) Floatglas oder Ziehglas, bevorzugt mit mindestens einem Netzwerkwandler und besonders bevorzugt mit Natriumoxid, Kaliumoxid, Kalziumoxid und/oder Magnesiumoxid, enthält. 6. Disc (10) according to any one of claims 1 to 5, wherein the glass sheet (1) float glass or drawing glass, preferably with at least one network converter and more preferably with sodium oxide, potassium oxide, calcium oxide and / or magnesium oxide.
7. Scheibe (10) nach einem der Ansprüche 1 bis 6, wobei die Glasscheibe (1 ) weniger als 0,2 Gew.-% Aluminiumoxid und/oder weniger als 0,02 Gew.-% Eisenoxid enthält. A disc (10) according to any one of claims 1 to 6, wherein the glass sheet (1) contains less than 0.2% by weight of alumina and / or less than 0.02% by weight of iron oxide.
8. Scheibe (10) nach einem der Ansprüche 1 bis 7, wobei die Glasscheibe (1 ) thermisch vorgespannt oder teilvorgespannt ist. 8. disc (10) according to any one of claims 1 to 7, wherein the glass sheet (1) is thermally toughened or teilvorgespannt.
9. Scheibe (10) nach einem der Ansprüche 1 bis 8, wobei die Glasscheibe (1 ) eine Dicke b von 1 mm bis 25 mm und bevorzugt von 2 mm bis 12 mm aufweist. 9. disc (10) according to any one of claims 1 to 8, wherein the glass sheet (1) has a thickness b of 1 mm to 25 mm and preferably from 2 mm to 12 mm.
10. Scheibe (10) nach einem der Ansprüche 1 bis 9, wobei die Schutzschicht (2) mindesten ein Dotierelement, bevorzugt Antimon, Fluor, Silber, Ruthenium, Palladium, Aluminium und/oder Tantal enthält und der Anteil des Dotierelements an dem metallischen Anteil der Schutzschicht bevorzugt von 0 Gew.-% bis 10 Gew.-% und besonders bevorzugt von 1 Gew.-% bis 5 Gew.- % beträgt. 10. Disc (10) according to any one of claims 1 to 9, wherein the protective layer (2) contains at least one doping element, preferably antimony, fluorine, silver, ruthenium, palladium, aluminum and / or tantalum and the proportion of the doping element to the metallic portion the protective layer is preferably from 0% by weight to 10% by weight and particularly preferably from 1% by weight to 5% by weight.
1 1 . Scheibe (10) nach einem der Ansprüche 1 bis 10, wobei zwischen der Glasscheibe (1 ) und der Schutzschicht (2) mindestens eine weitere Schicht (3) und bevorzugt eine Farbschicht, eine Infrarot-reflektierende Schicht, eine Anti- Reflexions-Schicht oder eine Low-E-Schicht, angeordnet ist. 1 1. Disc (10) according to one of claims 1 to 10, wherein between the glass pane (1) and the protective layer (2) at least one further layer (3) and preferably a color layer, an infrared-reflective layer, an anti-reflection layer or a low-E layer is arranged.
12. Verfahren zur Herstellung einer Scheibe (10), wobei mindestens: 12. A method for producing a disc (10), wherein at least:
a. eine Glasscheibe (1 ) mit einer erste Seite (I) und einer zweiten Seite (II) bereitgestellt wird und  a. a glass sheet (1) having a first side (I) and a second side (II) is provided and
b. eine Schutzschicht (2) auf die erste Seite (I) und/oder die zweite Seite (II) aufgebracht wird,  b. a protective layer (2) is applied to the first side (I) and / or the second side (II),
wobei die Schutzschicht (2) Zinn-Zinkoxid enthält.  wherein the protective layer (2) contains tin-zinc oxide.
13. Verwendung einer Schutzschicht (2) in einer Scheibe (10) nach einem der 13. Use of a protective layer (2) in a pane (10) according to one of
Ansprüche 1 bis 1 1 zur Vermeidung der Korrosion der Glasscheibe (1 ) bei Lagerung und Alterung, bevorzugt in mariner oder feuchter und besonders bevorzugt in feuchtwarmer Umgebung.  Claims 1 to 1 1 for preventing corrosion of the glass sheet (1) during storage and aging, preferably in marine or humid and particularly preferably in humid environment.
14. Verwendung einer Scheibe (10) als Teil einer Außenfassade oder Innenfassade eines Fensters in einem Gebäude oder in einem Fahrzeug zu Lande, zu Wasser oder in der Luft oder als Einbauteil in Möbeln und Geräten, besonders bevorzugt unter feuchten, feuchtwarmen und/oder marinen Bedingungen, insbesondere als Verglasung in Küstennähe oder auf dem Wasser, auf Booten oder Schiffen, in Schwimmbädern, Saunen oder Gewächshäusern. 14. Use of a pane (10) as part of an external facade or interior facade of a window in a building or in a vehicle on land, water or in the air or as a built-in part in furniture and appliances, particularly preferably under moist, moist and / or marine Conditions, in particular as glazing near the coast or on the water, on boats or ships, in swimming pools, saunas or greenhouses.
EP13791814.0A 2012-12-06 2013-11-15 Glass panel having at least one protective layer comprising tin-zinc oxide Pending EP2928838A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13791814.0A EP2928838A1 (en) 2012-12-06 2013-11-15 Glass panel having at least one protective layer comprising tin-zinc oxide

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12195855 2012-12-06
EP13791814.0A EP2928838A1 (en) 2012-12-06 2013-11-15 Glass panel having at least one protective layer comprising tin-zinc oxide
PCT/EP2013/073930 WO2014086570A1 (en) 2012-12-06 2013-11-15 Glass panel having at least one protective layer comprising tin-zinc oxide

Publications (1)

Publication Number Publication Date
EP2928838A1 true EP2928838A1 (en) 2015-10-14

Family

ID=47290772

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13791814.0A Pending EP2928838A1 (en) 2012-12-06 2013-11-15 Glass panel having at least one protective layer comprising tin-zinc oxide

Country Status (2)

Country Link
EP (1) EP2928838A1 (en)
WO (1) WO2014086570A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3017128A1 (en) * 2014-01-31 2015-08-07 Saint Gobain EASY CLEANING GLAZING COMPRISING AN EXTERNAL LAYER BASED ON TIN OXIDE AND ZINC
WO2017021590A1 (en) * 2015-07-31 2017-02-09 Saint-Gobain Glass France Bathroom glazing

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1378839A (en) 1963-04-16 1964-11-20 Saint Gobain Further training in sheet glass manufacturing
AU561315B2 (en) * 1984-10-29 1987-05-07 Ppg Industries Ohio, Inc. Sputtering films of metal alloy oxide
US4859532A (en) * 1986-11-27 1989-08-22 Asahi Glass Company Ltd. Transparent laminated product
US5397920A (en) * 1994-03-24 1995-03-14 Minnesota Mining And Manufacturing Company Light transmissive, electrically-conductive, oxide film and methods of production
CA2179853C (en) * 1995-06-26 2007-05-22 Susumu Suzuki Laminate
US6905991B1 (en) 1997-03-13 2005-06-14 Saint-Gobain Glass France Soda-lime-silica glass compositions and applications
DE19848751C1 (en) 1998-10-22 1999-12-16 Ver Glaswerke Gmbh Transparent substrate coating especially a low emissivity layer system with a silver functional layer for glass panes
FR2856627B1 (en) * 2003-06-26 2006-08-11 Saint Gobain TRANSPARENT SUBSTRATE WITH COATING WITH MECHANICAL STRENGTH PROPERTIES
JP4552950B2 (en) * 2006-03-15 2010-09-29 住友金属鉱山株式会社 Oxide sintered body for target, manufacturing method thereof, manufacturing method of transparent conductive film using the same, and transparent conductive film obtained
WO2012006748A1 (en) * 2010-07-16 2012-01-19 Gevartis Ag Method for improving heat-protection glazings by preventing glass corrosion caused by alkaline glass attack and by priming

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2014086570A1 *

Also Published As

Publication number Publication date
WO2014086570A1 (en) 2014-06-12

Similar Documents

Publication Publication Date Title
EP2822907B1 (en) Window pane for automobile with thermal radiation reflecting coating
DE69731268T2 (en) Glazing used for sun protection and / or thermal insulation, consisting of a substrate coated several times with thin layers
DE19541937C1 (en) Multilayer heat-insulating coating for glass - comprises silver@ layer, sacrificial metal layer, lower and upper de-reflection layers each comprising two different oxide layers
DE60131776T3 (en) GLAZING WITH THIN-CHAMBER STACK, WITH PROPERTIES FOR SUN PROTECTION AND / OR HEAT INSULATION
DE69813648T2 (en) Transparent substrate with at least one thin layer of silicon nitride or oxynitride and process for its production
DE69825398T2 (en) Transparent substrate with a thin-film structure with infrared reflashing properties
DE69912427T2 (en) TRANSPARENT SUBSTRATE WITH SILVER COATING
WO2015190111A1 (en) Multi-layered glass unit and glass plate for multi-layered glass unit
EP2958872A1 (en) Pane having a coating that reflects thermal radiation
WO2007115796A2 (en) Weather-resistant layer system
EP2928688B1 (en) Fire protection pane and flame retardant glazing
EP3148797B1 (en) Fire protection pane and flame retardant glazing
DE19616841B4 (en) Coated glassy material panel with high translucency, low solar factor and neutral appearance when reflected and used in a multiple glazing unit
EP2760665B1 (en) Fire protection element with protective coating, and method for producing the same
WO2014086570A1 (en) Glass panel having at least one protective layer comprising tin-zinc oxide
DE69833099T2 (en) Transparent substrates with an accumulation of layers with infrared and / or solar radiation reflecting properties
DE102011114669B3 (en) Coating system for solar control glass, solar control glass and process for the production of solar control glass
DE102015006644B4 (en) Laminated pane for protective glazing and its use, picture glazing and display glazing
DE3611844A1 (en) METHOD FOR PRODUCING A TEMPERED AND / OR BENDED GLASS DISC WITH PLATINUM COATING OR THE LIKE
DE69722543T2 (en) Thermally insulating glazing
WO2015025043A1 (en) Flat glass having a filtering effect
DE69921053T2 (en) GLASS WITH SUNSCREEN COATING
DE102005007826B4 (en) Transparent substrate with a heat-reflecting coating and method for its production
DE102009023161A1 (en) Method for the production of composite materials with an antireflexion coating, comprises applying a barrier layer on a glass substrate against sodium ion diffusion and applying a single-layer antireflexion coating over the barrier layer
DE102011118850A1 (en) Glass pane for motor car, has boundary faces having anti-reflection layer whose reflectivity for light in visible range is set to preset value and anti-fitting layer whose thermal emissivity is set to specific value, respectively

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20150518

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
RIN1 Information on inventor provided before grant (corrected)

Inventor name: KASPER, ANDREAS

Inventor name: LETOCART, PHILIPPE

Inventor name: RENIER, ANAIS

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SAINT-GOBAIN GLASS FRANCE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20210430

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS