Fire protection pane and flame retardant glazing

The invention relates to a fire-resistant window, in particular for fire-rated glazing, with a protective layer for reducing the opacification of the pane during aging. Furthermore, the invention relates to a method for producing this type of fire-resistant glazing and its use.

[0002] Fire gassing is known from various embodiments and is used, for example, in construction. They usually consist of two transparent load-bearing elements, such as glass panes, between which a fire-resistant layer is placed from a transparent, swellable ("foaming and swellable") material. From EP 0 620 781 B1, for example, a fire-fighting layer of a water-containing alkaline polysilicate is known. By the influence of heat on the fire-resistant glazing, the water contained in the alkaline polysilicate layer evaporates and the alkaline polysilicate becomes frothed. The transparency of the fire protection layer is then strongly reduced, especially in the case of thermal radiation, and protects for a certain time from unwanted entry of heat. A large extension of the fire layer usually leads to the splashing of one of the glass panes, and in particular to the glass panes directed to the source of the fire. Therefore, in order to improve the protection against heat and mechanical stability, a larger number of glass panes with lying between the fire layers are placed one behind the other.

[0003] Further improved alkali silicate based fire layers with an extremely high water content of 80% to 90% are known from EP 0 192 249 A2.

[0004] Fire protection glass and fire-rated glazing with this type of fire-protection layers show over time or point-to-spot haze in the perceptible region.

[0005] The object of the present invention is therefore to prepare a fire protection window that will exhibit better aging resistance, in particular limited cloudiness during aging. These and subsequent tasks are solved according to the invention proposed by means of a fire-resistant shaft with the features of the independent patent claims. Preferred embodiments of the invention are defined by the features of the additional claims.

[0006] The method of manufacturing fire-resistant glazing as well as the use of fire-resistant glazing arise from the following independent patent claims.

[0007] The fire-resistant pane according to the invention comprises

- at least one float glass pan with a side after tin bathing,

- at least one protective layer, which is assigned flat to the float glass pane from the side of its tin bath and

- at least one fire protection layer, which is assigned to a protective layer, wherein the protective layer comprises a metal oxide, a metal silicon and / or mixtures thereof or laminated joints.

The present invention is based on the inventors' knowledge that, depending on the quality of the glass, some float glass panes that have been in contact with the fire-protection layer after the tin bath have a marked opacification of transparency in the aging test by assigning a glass pane float and fire protection layer. On the other hand, it turned out that in the float glass panes, which were in contact with the fire protection layer on their atmospheric side, in the aging test they had no or only a slight transparency opacity. By placing a protective layer according to the invention between the side of a float glass pan having a tin bath and a fire protection layer, cloudiness in the aging test could be avoided or significantly reduced.

[0009] The invention can be understood in the following model: During manufacture, the tin-glass hot side of the hot pan is in contact with the tin bath. This leads to the development of a surface that, in contact with a typical alkaline fire layer depending on the morphology of the tin layer, corrodes heterogeneously and may give a cloudy appearance after aging. The atmospheric side of the float glass pane has in contact with the alkaline fire protection layer only a small homogeneous corrosion which does not lead to any or only a slight cloudiness. By applying the protective layer according to the invention, the corrosion of the side after bathing in the tin is reduced and unified during contact with the alkaline fire protection layer, so that there is no or only slight turbidity similar to the atmospheric side. [0010] In a preferred embodiment of the fire-protection glazing according to the invention, the fire-protection layer is alkaline.

[0011] The fire protection layer according to the invention preferably contains an alkali silicate and preferably an alkali polysilicate. Such fire protection layers are known for example from EP 620 781 B1 or EP 0 192 249 A2. Alternative fire protection layers comprise an alkaline phosphate, an alkaline tungstate and / or an alkaline molidate, as is known from DE 35 30 968 C2.

[0012] Further alternative fire layers comprise a hydrogel with a solid phase of a polymer and preferably a polyacrylamide or N-methylacrylamide, as is known from DE 27 13 849 C2, or a polymerized 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, as is known from DE 40 01 677 C1.

[0013] The thickness of the fire-protection layers can vary over a wide range and be adapted to the respective application requirements. Preferred fire layers exhibit a thickness h of 0.5mm to 7mm, preferably 1mm to 6mm, for silicates. In the case of hydrogels, these thicknesses are between 8mm and 70mm.

[0014] The protective layer comprises according to the invention at least one metal oxide, one metal nitride, one metal silicon and / or mixtures or layered joints thereof. The metal oxide is preferably non-crystalline. It may be preferably amorphous or partially amorphous (and thus partly crystalline), but not fully crystalline. This type of non-crystalline protective layer has the particular advantage that it exhibits limited roughness and thus forms a preferably smooth surface for the layers to be placed over the protective layer, where scratches and spot defects are filled.

[0015] The protective layer may comprise at least an oxide of one or more elements of tin, zinc, indium, tungsten, silicon, titanium, zirconium, hafnium and gallium. Alternatively, the protective layer may contain a nitride of one or more elements, such as tin, zinc, indium, tungsten, silicon, titanium, zirconium, hafnium and gallium. Alternatively, the protective layer may comprise a silicon of one or more elements such as tin, zinc, indium, tungsten, titanium, zirconium, hafnium and gallium.

[0016] In a preferred embodiment of the fire protection glazing according to the invention, the protective layer comprises admixtures, for example antimony, fluorine, silver, ruthenium, palladium, aluminum and tantalum. The proportion of admixture in the metallic part of the protective layer in percent by mass (% m / m) is preferably from 0% m / m to 10% m / m, and particularly preferably from 1% m / m to 5% m / m. Fire protection glass with protective layers, which show this type of admixture, showed a particularly low cloudiness during aging.

[0017] In a preferred embodiment of the fire protection glazing according to the invention, the protective layer comprises tin oxide, zinc oxide or mixed tin and metal oxide. The protective layer contains especially preferably tin oxide or a mixed tin-zinc oxide. Fire protection glazings with protective layers that contain tin have a particularly low cloudiness during aging.

In a preferred embodiment of the fire protection glazing according to the invention, the protective layer comprises tin-zinc oxide in a ratio of zinc: from 5% m / m: 95% m / m to 95% m / m: 5% by weight. and preferably from 15% m / m: 85% - weight to 70% m / m: 30% m / m. The tin-zinc oxide protective layers with this type of mixture ratios are particularly resistant and show especially low turbidity during aging.

[0019] In a preferred embodiment of the fire protection glazing according to the invention, the protective layer comprises SnZnyOz with 0 <z <(y + 2x) and preferably 0.7 * (y + 2x) <z <(y + 2x) and particularly preferably 0, 9 * (y + 2x) <z <(y + 2x). The tin-zinc oxide protective layers with this type of mix ratio are particularly resistant and show particularly low turbidity during aging. In a particularly preferred embodiment of the fire protection glass according to the invention, the protective layer has ZnSnO3 or ZnSnO4 or mixtures thereof. The tin-zinc oxide protective layers with this type of mix ratio are particularly resistant and show especially low turbidity during aging.

In a preferred embodiment of the fire protection shaft according to the invention, the protective layer consists of tin-zinc oxide, as well as optionally of doping metal and admixtures depending on the production conditions. The tin-zinc oxide protective layers with this type of mixture ratio are particularly resistant and have little cloudiness during aging.

[0020] Separation of the mixed tin and zinc oxide takes place, for example, when oxygen is added as a reaction gas during sputtering ("Kathodenzerstaubung").

[0021] In a preferred embodiment of the protective layer according to the invention, the thickness of the layer d of the protective layer is from 2nm to 500nm, preferably from 3nm to 50nm, particularly preferably from 5nm to 30nm. In a two-layer or multilayer protective layer, this particularly applies to the total thickness of the protective layer. Fire protection glass with a protective layer with such layer thicknesses showed particularly low cloudiness during aging.

In the fire protection shaft according to the invention, the protective layer is formed as a multilayer and preferably as a two-layer combination of layers as defined in claim 1. A protective layer of metal nitride, in particular silicon nitride and metal oxide is preferred, especially above of the mixed oxide tin - zinc or doped mixed tin - zinc oxide. These two-layer protective layers have proven to be extremely resistant to alkaline fire protection layers and exhibit even less turbidity during aging than monolayer protective layers.

[0023] As the research on the invention has shown a two-layer protective layer with a (partial) metal nitride protection layer, in particular silicon nitride, the advantage that the second (partial) metal oxide layer, in particular zinc-zinc oxide can be made more sharply , than in a monolayer protective layer of metal oxide. Such double layer protective layers are also particularly resistant to alkaline fire protection layers and show little cloudiness during aging.

[0024] The action according to the invention occurs when the (partial) silicon nitride protective layer has a thickness of only a few nanometers, preferably 1nm to 15nm, especially preferably from 3nm to 10nm.

The synergistic interaction of the silicon nitride layer with the tin-zinc oxide layer even allows that the second (partial) protective layer of tin-zinc can be so reduced that the overall thickness of the layer of the two-layer protective layer can be chosen as thinner than the layer Protective one layer of tin-zinc oxide, with constant good strength against the fire protection layer. Reducing the total thickness of the protective layer can improve the optical properties of the fire-resistant pane as well as increase the transparency and reduce the color deviation. Metal nitride layers, in particular silicon nitride layers, are very simple and cheap to produce in terms of process technology and have high optical transparency.

[0026] In a preferred embodiment, the (partial) silicon nitride protective layer is placed directly on the side after bathing in a tin glass float, and a (partial) protective layer of tin-zinc oxide is placed on the (partial) silicon nitride layer . It is understood that the order of the materials can also be changed, so that the (partial) protective layer of tin-zinc oxide is placed directly on the float side of the tin in a tin and a (partial) silicon nitride protective layer is placed on the side (partial) protective layer of tin-zinc oxide.

[0027] The float glass pane according to the invention is made using the float method. Such methods are known, for example, from FR 1 378 839 A. During the production of float glass in a continuous process, the molten glass in a liquid-dough form is continuously fed on one side to a longitudinal liquid tin bath. Molten glass floats in a tin bath and a uniform layer of glass spreads. Thanks to the surface tension of tin and liquid glass, a very smooth surface is created. At the back end of the tin bath, the molten glass is cooled and solidified. In the context of the present invention, the side of a float glass pan that during its production floats on a tin bath is referred to as the side after bathing in tin. The side facing the side of the float glass window after tin bathing is referred to as the atmospheric side. The float glass panel contains or preferably consists of boro-silicate glass, aluminum-silicate glass or glass of alkaline earth metal silicates ("Erdalkali-Silikatglas"), and especially preferably calcium-lime glass, and particularly preferably calcium-glass. - sodium in accordance with EN 572-1: 2004.

[0028] The glass panes of the float type are preferably thermally pre-stressed or partially stressed. The thermally partially stretched or stressed glass of float glass preferably has a stress of 30 MPa to 200 MPa, particularly preferably 70 MPa to 200MPa. This type of tensioned or partially tensioned float glass panes are known for example from DE 197 10 289 C1. Thermally stretched or partially tensioned float glass panes are suitable due to their higher stability for fire protection glazing and the protective layer according to the invention is particularly advantageous.

[0029] The thickness of the float glass panes can vary over a wide range and thus be perfectly adapted to the requirements of individual cases. Preferably, panes with a standard thickness of 1mm to 25mm, preferably 2mm to 12mm, are used. The size of the pane can vary over a wide range and is directed to the size of the application according to the invention.

[0030] The float glass panes may have any three-dimensional form. Preferably, the three-dimensional form has no shadow zones, so that it can be covered by a layer in the sputtering process. Preferably the pane is planar or bent slightly or strongly in the direction or in many directions of the room. The float glass can be colorless or colored.

[0031] The float glass pane according to the invention may consist of a combination of two or more individual float glass panes that are connected to one another by means of at least one intermediate layer. The intermediate layer preferably comprises a thermoplastic plastic such as polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), polyurethane (PU), polyethylene terephthalate (PET), or a greater number of layers of such a compound, preferably having a thickness of 0.3 mm to 0,9mm.

In a preferred embodiment of the fire protection glazing according to the invention between the protective layer and the fire-protection layer, at least one adhesion-improving layer or one adhesion-reducing layer is provided. The adhesion promoter layer contains, for example, organically hydrophilic substances based on silanes, titanates or zirconates and is known, for example, from EP 0 001 531 B1 and EP 0 590 978 A1. The adhesion-promoting layers include, for example, hydrophobic silanes with organic functional groups, such as fluoroalkylsilanes, perfluoroalkylsilanes, fluoroalkyltrichloro-silanes, fluoroalkylalkyl alkoxysanes, perfluoroalkylalkoxy silanes, fluoroaliphatic silyl ethers, alkylsilanes and phenylsilanes and silicones. Such hydrophobic silanes with organic functional groups are known from DE 197 31 416 C1. Alternative adhesion-reducing layers contain polymer waxes, preferably based on polyethylene.

[0033] In a preferred embodiment of the fire protection glazing according to the invention, a at least one further layer is placed between the side after bathing in the tin of the float glass and the protective layer, which affects, for example, the optical properties of the fire-resistant window. This type of subsequent layer, for example, increases the permeability through the fire-resistant glass, reduces reflections or gives the transmitted light a color.

[0034] The protective layer is preferably permeable to electromagnetic radiation, primarily electromagnetic radiation with a wavelength of from 300nm to 1300nm, and in particular for visible light. "Permeable" means that the total permeability has a permeability through the layered float glass with more than 50%, preferably more than 70%, and more preferably more than 90%.

[0035] The invention further comprises a fire protection glazing which includes at least

- a fire protection glass according to the invention; and

- a second float glass with an atmospheric side and a side after a tin bath, where the second glass of float glass is flush with the fire protection glass layer by means of an atmospheric side. An alternative embodiment of the fire protection glazing according to the invention comprises at least

- a fire protection glass according to the invention; and

- a second float glass with an atmospheric side and a tinned side, where the second float glass has a second, protective layer on the side after the tin bath, and the second glass of float is connected flat by a second protective layer with fire-fighting glass layer.

[0036] In a further preferred fire-protection glazing according to the invention, the atmospheric side of a glass pane of a fire-extinguishing window is flush with the second fire-protection layer and the second fire-protection layer is connected to the atmosphere of the third pane of float glass.

[0037] In an alternative further embodiment of the fire protection glazing according to the invention, the atmospheric side of the glass of the fire-resistant glass pane is flush with the second fire-protection layer and the second fire-protection layer joined by another protective layer with the tin-etched side of the third glass pane of glass type float.

[0038] Such triple glazing has particularly high stability and fire protection. It is understood that, according to a similar principle, fire protection glazing with four or more float glass panes is also manufactured, where for preventing the opacity of transparency during aging, between each fire layer and directly adjacent to it after bathing in a tin panes of float glass are provided with a protective layer according to the invention.

Immediately adjacent means here that there is no glass pane between the party after bathing and the fire-fighting layer.

[0039] The invention further comprises a fire protection glazing consisting of a stack consisting of a first float glass, a first fire layer, a second float glass, a second fire layer and finally a float glass, where between each side after bathing in a tin, and a directly adjacent fire protection layer, a protective layer according to the invention is placed.

[0040] In a further embodiment of the fire-protection glazing according to the invention, at least one further glass of float glass and one further fire-protection layer within the stack are placed. It is understood that between each side after bathing in a tin another glass of float glass and a directly adjacent fire protection layer is another protective layer according to the invention.

[0041] To protect the fire protection glazing, and in particular the fire protection layer against heat and UV rays, the fire protection glazing, and in particular the outward-looking glass from the float glass may have additional functional layers with UV and / or infrared reflection. In addition, a larger number of fire-resistant glazing can create insulating glazing thanks to vacuum or gas filled intermediate spaces.

[0042] The invention includes a method for manufacturing fire-resistant glazing, wherein at least:

a. on the side after bathing in the tin of the first glass of float glass a protective layer is applied,

b. the first float glass panes and the second float glass panes are maintained at a constant distance, so that a forming cavity forms between the side after the tin bath of the first float glass panes and the second float glass panes.

c. the fire-fighting layer in liquid form is poured into the molding cavity and hardened.

In a preferred embodiment of the method according to the invention, the steps will be repeated in such a way that the third glass of float glass is maintained with a constant distance to the first or second float glass and the forming cavity thus formed is filled with the second glass. fireproof layer. This step may also take place in parallel, i.e. that three or more float glass panes can be simultaneously maintained with a gap, and the fire layers are formed by pouring an aqueous solution of a silicate or hydrogel. It is understood that the method of developing fire-resistant glazing consisting of a plurality of panes with four or more float glass panes can be carried out by appropriate repetition.

[0044] The application of the protective layer in step (a) may take place by a known method, preferably by sputtering supported by a magnetic field. This is particularly advantageous due to the simple, quick, cheap and even coating of the float glass.

[0045] A method for producing mixed tin and zinc oxide layers by reactive cathodic sputtering is known for example from DE 198 48 751 C1. The mixture of tin and zinc oxide is preferably separated by means of a target which contains from 5% m / m to 95% m / m zinc, from 5% m / m to 95% m / m tin and from 0% m / m to 10 % m / m of antimony, as well as additives dependent on production. Target especially preferably contains from 15% m / m to 70% m / m zinc, from 30% m / m to 85% m / m tin and from 0% m / m to 5% m / m antimony, as well as admixtures of other metals dependent on production. Separation of the mixed tin and zinc oxide takes place, for example, when oxygen is added as a reaction gas during sputtering.

[0046] The protective layer may alternatively be applied by evaporation, chemical vapor deposition (CVD), plasma assisted vapor deposition (PECVD), by a sol-gel ("Sol-Gel-Verfahren") process, or methods of wet chemistry ("nasschemische Verfahren").

[0047] In step (b), a first float glass pane and a second float glass pane are maintained at a constant distance such that a forming cavity forms. This may take place, for example, thanks to the spacer, which are preferably located in the edge area of ​​the float glass panes. The spacers can remain as a fixed component in the fire-resistant glazing or be removed. Alternatively, the float glass panes can be held in position due to the outer handles.

[0048] In step (c), a pourable solution of the fire-fighting layer is poured into the forming cavity and cured to the fire-fighting layer. In the case of a fire protection layer comprising a water-containing alkaline polysilicate, the alkali silicate is for example combined with a hardener that contains or releases silicon dioxide. The loose mold thus formed is poured into the forming cavity. There, the mass hardens, while maintaining the water content, into a solid layer of polysilicate. Methods for making a fire protection layer of a hydrogel are known, for example, from WO 94/04355 or DE 40 01 677 C1.

In a preferred further embodiment of the method according to the invention, before the first step (a) or between step (a) and (b) a first glass panes of float and / or a first glass of float glass, as well as a second glazing with float glass is thermally stressed or partially stressed.

[0050] The invention further comprises the use of a protective layer between the tinfoam side and the fire protection layer, in particular the alkaline fire protection layer, in order to reduce the cloudiness of the float glass during aging.

[0051] The invention further includes the use of a fire-resistant pane as a structural element, as a division of rooms, as part of an external façade or window in a building or land, water or air vehicle or as an element embedded in furniture or devices.

[0052] The invention is explained below using a drawing and an example. The drawing is not fully consistent with the scale. The invention is in no way restricted by drawing. shown:

Fig. 1 shows a schematic representation in cross-section of a fire-resistant pane according to the invention,

Fig. 2A shows a schematic cross-sectional view of the fire protection glazing according to the invention,

Fig. 2B is a schematic cross-sectional representation of an alternative embodiment of the fire protection glazing according to the invention,

Fig. 3 a schematic cross-sectional representation of an alternative embodiment of the fire protection glazing according to the invention,

Fig. 4A shows a cross-sectional representation of an alternative embodiment of the fire protection glazing according to the invention,

Fig. 4B a schematic cross-sectional representation of an alternative embodiment of a fire-resistant glazing according to the invention,

Fig. 5 is a block diagram of an embodiment of the method according to the invention,

Fig. 6 is a turbidity diagram according to the invention of a fire protection window compared to the state of the art,

Fig. 7 is a schematic cross-sectional representation of another alternative embodiment of the fire-protection glazing according to the invention and

Fig. 8 is a schematic cross-sectional representation of another alternative embodiment of the fire protection glazing according to the invention.

[0053] Fig. 1 shows a schematic representation of the fire protection window 10 according to the invention in cross-section. The fire pane 10 includes a glass of float 1.1 with an atmosphere 1 side and a side after a bath of zinc II. The float 1.1 glass pane has, for example, a thickness b of 5mm and a size of 2m x 3m. It is understood that the float 1.1 glass panes can also have other thicknesses and dimensions suited to the respective application.

[0054] On the side after bathing in the tin II of the float 1.1 glass, a protective layer 3.1 is placed flat. On the protective layer 3.1, there is a 3.1 fireproof layer of alkaline polysilicate. The protective layer 3.1 extends partially and preferably substantially as a whole through the whole side after bathing in the tin II of the float 1.1 glass. The protective layer 3.1 extends in particular through the entire plane between the fire protection layer 2.1 and the float 1.1 glass. As a result, it can be guaranteed that the surface of the side after bathing in the tin II of the float 1.1 glass pane is protected by the alkaline polysilicate of the fire protection layer 2.1.

[0055] The protective layer 3.1 comprises, for example, tin-zinc oxide with an antimony admixture and was isolated by means of sputtering. The target for the release of the protective layer 3.1 contained 30% m / m zinc, 68% m / m tin and 2% m / m antimony. The separation occurred after the addition of oxygen as the reaction gas during sputtering. The thickness d of the protective layer 3.1 is, for example, 25nm.

[0056] The fire-fighting layer 2.1 comprises, for example, a hardened polysilicate which is formed of an alkaline silicate and at least one hardener, for example potassium silicate and colloidal silicic acid. In an alternative embodiment, potassium silicate can be made directly from potassium hydroxide and silicon dioxide. In polysilicates, a molar ratio of silicon dioxide and potassium oxide (SiO2: K2O), for example 4.7: 1. This type of fire protection layer 2.1 is usually alkaline with a pH value of 12. The thickness h of the fire protection layer 2.1 is, for example, 3 mm.

Fig. 2A shows a schematic cross section of the fire protection glazing 100 according to the invention. The fire protection glazing 199 according to the invention includes, for example, the fire protection panel 10 according to the invention described in Fig. 1. Furthermore, the fire-fighting layer 2.1 of the fire-protection pane 10 on the side opposite to the layer protective device 3.1 is flush with the other glass of float 1.2 from its atmospheric side. The properties of the second float glass panel 1.2 correspond, for example, to the properties of the float 1.1 glass pane.

[0058] Fig. 2B shows a schematic cross section of an alternative embodiment of the fire protection glazing 100 according to the invention. The fire protection glazing 100 according to the invention corresponds to the glazing of Fig. 2A. To improve the properties in case of fire between the protective layer 3.1 and the fire protection layer

2.1, as well as between the fire-protection layer 2.1 and the second glass of float 1.2, the adhesive-reducing layer 4 is placed. The adhesive-reducing layer 4 comprises, for example, an organic-functional silane with hydrophobic action. The adhesion reduction layer 4 has the particular advantage that in the event of a fire when the glass of float 1.1, 1.2 is broken, individual fragments can be detached from the fire layer 3.1, while the combination of the fire-protection layer 3.1 will not be lost.

[0059] Fig. 3 shows a schematic cross section of an alternative embodiment of the fire protection glazing 100 according to the invention. The fire protection glazing 100 according to the invention includes, for example, the fire protection panel 10 according to the invention, which is described in Fig. 1. Furthermore, the fire protection layer 2.1 of the fire pane 10 it is flushly connected on the side opposite to the protective layer 3.1 by means of a second protective layer 3.2 with a side after bathing in the tin II of the second glass of float 1.2. The second glass of float 1.2 and the second protective layer 3.2 form with the fire protection layer 2.1 again according to the invention fire protection glass

10.1. in that, both side after bathing in the tin II of glass from 1.1 glass, as well as the side after bathing in the tin II of the second glass of float 1.2 are separated by means of protective layer 3.1, 3.2 from the fire-fighting layer 2.1, are prevented in accordance with the invention, turbidity of transparency by fire-resistant glazing during aging.

[0060] This type of fire protection glazing 100 is suitable for independent use as a building element in a building or as glazing in a vehicle.

[0061] Fig. 4A shows a schematic cross-sectional representation of an alternative embodiment of the fire protection glazing 101 according to the invention, on the example of triple glazing with three float glass panes 1.1, 1.2, 1.3 and two fire protection layers 2.1, 2.2. The fire protection glazing 101 according to the invention comprises, for example, a fire protection panel 10 according to the invention, which is described in Fig. 1. Furthermore, the fire protection layer 2.1 is flatly connected on the opposite side with respect to the protective layer 3.1 with the atmospheric aspect of the second float glass 1.2. . The second float glass 1.2 has on the side after bathing in the tin II a second protective layer 3.2 and it is connected with the second fire protection layer 2.2. The second float glass 1.2,

3.2 is connected to the atmospheric side I of the third glass of float 1.3.

[0062] Fig. 4B shows an alternative embodiment of the glazing 101 according to the invention. The fire layer 2.1 according to the invention of the fire pane 10 is flatly connected to the atmospheric side I of the second pane of float glass 1.2. In addition, the atmospheric side I of the float 1.1 glass panes is flat with the second fire protection layer 2.2. The second fire layer 2.2 is flush with the atmospheric side I of the third glass of float 1.3. This embodiment has the particular advantage that only one protective layer according to the invention is necessary

3.1, to create an aging-resistant fire-resistant glazing 101, since due to the appropriate alignment of the float glass windows 1.2, 1.3 only the side after bathing in the tin II of the float 1.1 glass pane adheres directly and is sepa- rately sealed with glass. fireproof layer 2.1.

[0063] The triple glazing illustrated in Figs. 4A and 4B shows particularly high stability and fire protection. It is understood that, according to a similar principle, fire protection glass with four or more float glass panes is also manufactured, avoiding the opacity of the transparency during aging between each fire layer and the immediately adjacent side after bathing in a tin glass pane. The protective layer according to the invention is placed in the float type.

[0064] The fire protection pane 10,11 and the fire protection glazing 100,101 of the embodiments shown herein may comprise further known and not shown spacers between adjacent float glass windows 1.1, 1.2, 1.3 and edge sealers around fire layers 2.1, 2.2. Suitable edge sealing materials include, for example, polyisobutylene as a spacer and a polysulphide, polyurethane or silicone as edge glue.

[0065] Fig. 5 shows a block diagram of an embodiment of the fire protection glazing 100 according to the invention 100 according to Fig. 2.

[0066] Fig. 6 shows the cloudiness chart of an aging test of the fire protection glazing units according to the invention in comparison to a fire screen according to the prior art as a comparative example. In the accelerated aging test, a suitable float glass was immersed for 4 hours and at a temperature of 80 ° C in an aqueous solution of potassium silicate. The aqueous solution of potassium silicate is an alkaline component in the preparation of the fire protection layer according to the invention from an alkaline polyisilicate hydrogel. The turbidity was measured using a BYK-Gardner haze-gard plus haze device.

[0067] Example 1 is a float glass according to the invention, whose side after bathing in tin II is covered with a protective layer of tin-zinc oxide. The ratio of tin to zinc was 50% m / m: 50% m / m. The thickness d of the protective layer was 25nm. After the test for aging, the measured turbidity was 0.3%.

[0068] Example 2 is a float glass according to the invention, the side of which after bathing in tin II was covered with a protective layer of zinc oxide. The thickness d of the protective layer was 25 nm. After the test for aging, the measured turbidity was 0.7%.

[0069] Example 3 is a float glass according to the invention, the side of which after bathing in the tin II was coated with an indium tin oxide (ITO) protective layer. The ratio of indium to tin was equal to 90% m / m: 10% m / m. The thickness d of the protective layer was 25 nm. After the aging test, the measured turbidity was 0.4%.

A comparative example according to the prior art was a float glass pane in which both the atmospheric side I and the side after bathing in the tin II were not covered with the layer and therefore both sides were under the influence of aqueous solutions of potassium silicate. After the test for aging, a turbidity of 8.9% was measured in the comparative example.

[0071] In the above-mentioned test for aging, the atmospheric sides I float glass of examples 1 to 3 and the comparative example were not protected by the protective layer according to the invention and thus exposed directly to an aqueous solution of potassium silicate. From this it can be concluded that the main reason for the cloudiness is the contact side after bathing in the tin II with an aqueous solution of potassium silicate.

[0072] Each of the protective layers according to the invention of Examples 1 to 3 reduces the haziness of the float glass pane as compared to the comparative example according to the prior art without the protective layer 3 according to the invention to a value of <1%. In the protection layer according to the invention of tin-zinc oxide according to example 1, the turbidity was reduced by 89 times. This result was unexpected and surprising for the expert.

[0073] Fig. 7 shows a schematic representation of an alternative embodiment of the fire protection window 10 in cross-section according to the invention. The float 1.1 glass panes and the fire protection layer 2.1 are formed in accordance with Fig. 1. The protective layer 3.1 is formed as a two-part layered structure of the (partial) protective layer 3.1a and the second (partial) layer 3.1b. The partial protective layer 3.1a has a thickness da of e.g. 8 nm and consists for example of a silicon nitride layer, in particular Si 3 N 4. (Partial) layer 3.1b has a denier of 15nm, for example, and consists of, for example, a tin-zinc oxide layer as described in Fig. 1. The thickness d of the total protective layer is thus 23nm.

[0074] As shown by the inventors' research, with the aid of a (partial) protective layer 3.1 a of silicon nitride, which has a thickness of 3 nm, advantageously increased resistance to aging and severely limited turbidity have been achieved. At the same time, the thickness of the tin-zinc oxide layer could be reduced without deterioration in aging or cloudiness.

[0075] In this embodiment (partial) protective layer 3.1az silicon nitride is placed directly on the side after bathing in the tin II of the glass of float 1.1, and the (partial) protective layer 3.1b zinc tin oxide is placed on (partial ) protective layer 3.1 of silicon nitride. It is understood that the order of the materials can also be changed, so that the layer of tin-zinc oxide can be placed directly on the side after bathing in a tin glass of float glass, and the layer of silicon nitride on a layer of tin-zinc oxide.

[0076] Figure 8 shows another alternative embodiment of the fire glazing 101 according to the invention 101. The fire protection glazing 101 of Fig. 8 corresponds to the fire protection glazing 101 of Fig. 4b, where only the protective layer 3.1 of Fig. 4b is made as a two-layer structure. layers: one (partial) protective layer 3.1 and one (partial) protective layer 3.1b. (Partial) protective layers 3.1a and 3.1b correspond, for example, to the layers of figure 7.

[0077] Table 1 shows the accumulated results of tests for aging and turbidity tests of various embodiments of fire protection glassware according to the invention 10.

Table 1

<td>Layered material</td><td>Thickness / thickness layer</td><td>Resistance in the test for aging</td><td>turbidity</td>

<td>tin oxide - zinc (3.1)</td><td>25nm (3.1)</td><td>good</td><td>little</td>

<td>azotek krzemu (3.1a) / tin oxide - zinc (3.1b)</td><td>8nm (3.1a) / 15nm (3.1b)</td><td>very good</td><td>very small</td>

<td>azotek krzemu (3.1a) / tin oxide - zinc (3.1b)</td><td>3nm (3.1a) / 15nm (3.1b)</td><td>good</td><td>little</td>

<td>azotek krzemu (3.1a) / tin oxide - zinc (3.1b)</td><td>15nm (3.1a) / 8nm (3.1b)</td><td>very good</td><td>very small</td>

[0078] In the first column of table 1 the material of the protective layer 3.1 is given, and in the second column the thickness of its layer. Protective layers 3.1 are placed directly on the glass of float 1.1. The value of silicon nitride (3.1a) / zinc tin oxide (3.1b) determines that the protective layer 3.1 consists of a two-layer layered structure. The first (partial) protective layer 3.1a of the silicon nitride given here is placed directly on the glass of float 1.1 and the second (partial) protective layer 3.1b of zinc oxide is placed directly on the first (partial) protective layer 3.1a. For the order of the layer of tin oxide - zinc (3.1b) / silicon nitride (3.1a), the reverse order applies.

[0079] It has been surprising that the sequence of silicon nitride (3.1a) / tin-zinc oxide (3.1b) with thicknesses of 3nm for the first (partial) protective layer 3.1a and 15nm for the second (partial) protective layer 3.1b showed similarly good aging resistance and low turbidity, like a monolayer protective layer 3.1 with 25nm tin oxide - zinc, although the total layer thickness could be reduced from 25nm to 18nm. In the combination of layer thicknesses of 8nm for silicon nitride and 15nm for tin-zinc oxide, experiments have shown even increased resistance to aging and less turbidity than in the single layer layer 3.1 of 25nm tin-zinc.

As has been found by the inventors' extensive testing, the combination of a metal nitride layer, such as silicon nitride, and a metal oxide layer, such as tin-zinc oxide, is particularly advantageous to form an aging-resistant fire-resistant glazing and to prevent clouding of the side after bathing. tin panes of float glass when in contact with the alkaline fire protection layer.

[0081] This result was unexpected and surprising to the expert.

List of symbols [0082]

1, 1.1, 1.2, 1.3 2, 2.1, 2.2 3, 3.1, 3.2, 3.3 3.1a, 3.1b 4

10, 10.1, 11

100, 101 float glass, fire protection layer, protective layer (partial) protective layer, protective layer, layer, glass, adhesion barrier, fire protection glass, fire protection glazing

And the side of the atmospheric float glass

Second side after tin bath b glass panel thickness d, da, db thickness of the protective layer h thickness of the fire protection layer

Saint - Gobain Glass France, France Plenipotentiary:

EP 2 928 688 B1-15137