Fire protection pane and flame retardant glazing

0001The present invention relates to refractory glazing, including a protective layer for reducing fogging of the glazing due to aging, especially for refractory glazing assemblies. Furthermore, the present invention relates to a method for manufacturing the refractory glazing assembly and its use.

0002Refractory glazing assemblies are known in various embodiments and are used, for example, in the building industry. Generally, a refractory glazing assembly consists of at least two transparent supporting elements, such as two flat glazings, between which a refractory layer of transparent expansive material is placed. For example, according to EP 0 620 781 81, a refractory layer made of water-containing alkaline polysilicate is known. Under the action of heat on the fire-resistant glazing assembly, the water contained in the alkaline polysilicate layer evaporates and the alkaline polysilicate foams. This greatly reduces the transparency of the refractory layer, especially due to heat radiation, and protects it from unwanted heat passage for some time. In general, a large expansion of the refractory layer causes one scattering of the plate glass, and in particular, the scattering of the plate glass on the ignition source side. As a result, in order to improve thermal protection and mechanical stability, a plurality of flat glass sheets are laminated and arranged via a refractory layer.

0003For example, from EP 0 192 249 A2, there are other known improved refractory layers based on alkali silicates with a particularly high water content of 80% to 90%.

<p num="0004"> Refractory glass and refractory grade glazing assemblies that include such refractory layers often show cloudy areas or areas in the visible range over time.</p><p num="0005"> It is an object of the present invention to provide a refractory glass with improved aging resistance and, in particular, reduced fogging during aging. According to the proposal of the present invention, this and other objects are achieved by refractory glass with the characteristics of independent claims. Advantageous embodiments of the invention are indicated by the characteristics of the dependent claims.</p><p num="0006"> The method for manufacturing a refractory glazing assembly and the use of refractory glass are described by other independent claims.</p>

<p num="0007"> The refractory glass according to the invention includes at least one float plate glass having a tin bath side and at least one protective layer arranged in a plane on the tin bath side of the float plate glass, and both the float plate glass and the protective layer are included. Heat-strengthened or partially-strengthened, the refractory glass further comprises at least one refractory layer arranged planarly on the protective layer, which is a metal oxide, metal nitride, metal silicate, and /. Alternatively, containing a mixture or layered compound of these, the refractory glass further comprises at least one end seal placed directly on the protective layer.</p><p num="0008"> In an advantageous embodiment, the end seals are arranged along the perimeter of the float glass and / or so as to surround a refractory layer on the float glass.</p><p num="0009"> The end seal preferably contains or comprises a sealant or adhesive mainly composed of polysulfides, polyurethanes, polysilicones, or reactive hot melts.</p><p num="0010"> Surprisingly, as revealed by our studies, the end seals can be placed directly on the float glass according to the invention along with the protective layer. This is because the protective layer is particularly tightly bonded to the float glass by being both strengthened or partially strengthened. On the contrary, in the float plate glass according to the prior art which is strengthened before the application of the protective layer and then coated by the protective layer, the problem of adhesion between the end seal and the float plate glass and the defect of the seal sealability are remarkable. Therefore, in the case of the float plate glass, it is usually necessary to first remove the protective layer in the end region before the end seal is applied.</p><p num="0011"> Another aspect of the present invention is that in the aging test, depending on the quality of the glass, a part of the float plate glass whose tin bath side is in contact with the refractory layer has a large visibility due to the arrangement of the float plate glass and the refractory layer. It is based on the findings of the inventors that it showed cloudiness. On the contrary, in the case of the float plate glass whose atmospheric side was arranged so as to be in contact with the refractory layer, the aging test showed no or little fogging of the field of view. It has been found that by introducing the protective layer according to the present invention between the tin bath side of the float plate glass and the refractory layer, it is possible to prevent or significantly reduce the fogging of the visual field in the aging test.</p><p num="0012"> The present invention can be understood by the following model. During production, the tin bath side of the hot float plate glass comes into contact with the tin bath. As a result, depending on the structure of the tin layer, a surface that corrodes non-homogeneously is formed, typically during contact with the alkaline refractory layer, which can give a cloudy appearance after aging. The atmospheric side of the float glass shows only some homogeneous corrosion when in contact with the alkaline refractory layer, resulting in no or little fogging. By introducing the protective layer according to the present invention, corrosion on the tin bath side during contact with the alkaline refractory layer is suppressed and becomes homogeneous, so that cloudiness is observed at all or little as on the atmospheric side.</p><p num="0013"> In an advantageous embodiment of the refractory glass according to the invention, the refractory layer is alkaline. The refractory layer according to the invention preferably contains an alkaline silicate, preferably an alkaline polysilicate. Such refractory layers are known, for example, by EP 0 620 781 81 or EP 0192249 A2. Alternative fireproof layers contain alkaline phosphates, alkali tungstates, and / or alkaline morphdenates, as known by DE 35 30 968 C2.</p><p num="0014"> Other alternative fireproof layers have a solid phase consisting of a polymer, as known by DE 27 13 849 C2, which polymer is preferably a hydrogel or DE, which is polyacrylamide or N-methylolacrylamide. As known by No. 40 01 677 C1, it contains a polymerized 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride.</p><p num="0015"> The thickness of the refractory layer is widely variable and can be adapted to each requirement of intended use. The advantageous refractory layer has a thickness h of 0.5 m to 7 mm, preferably 1 mm to 6 mm in the case of silicate. For hydrogels, the thickness is between 8 mm and 70 mm.</p><p num="0016"> According to the invention, the protective layer contains at least one metal oxide, one metal nitride, one metal silicide, and / or a mixture or layered compound thereof. The metal oxide is advantageously amorphous. The metal oxide can preferably be amorphous or partially amorphous (and thus partially crystalline), but is not completely crystalline. In particular, such a non-crystalline protective layer has only a small amount of roughness, which is said to form an advantageously smooth surface for the layer applied over the protective layer, filling in scratches and spot defects. Has advantages.</p><p num="0017"> The protective layer can contain, for example, at least one oxide of one or more of the elements tin, zinc, indium, tungsten, silicon, titanium, zirconium, hafnium, and gallium. Alternatively, the protective layer can contain one or more nitrides of tin, zinc, indium, tungsten, silicon, titanium, zirconium, hafnium, and gallium elements. Alternatively, the protective layer can contain one or more silicides of tin, zinc, indium, tungsten, titanium, zirconium, hafnium, and gallium elements.</p><p num="0018"> In an advantageous embodiment of the fireproof glass according to the invention, the protective layer contains, for example, antimony, fluorine, silver, ruthenium, palladium, aluminum, and tantalum dopants. The portion of the protective layer in weight percent (% by weight) of the dopant in the metal portion is preferably from 0% to 10% by weight, particularly preferably from 1% to 5% by weight. Refractory glass containing a protective layer having such a dopant shows little fogging, especially during aging.</p><p num="0019"> In an advantageous embodiment of the refractory glass according to the invention, the protective layer contains tin oxide, zinc oxide, or a mixed tin oxide-metal. The protective layer very particularly preferably contains tin oxide or mixed tin oxide-zinc. Refractory glass with a protective layer containing tin shows little fogging, especially during aging.</p><p num="0020"> In an advantageous embodiment of the fireproof glass according to the invention, the protective layer is 5% by weight: 95% by weight to 95% by weight: 5% by weight, preferably 15% by weight: 85% by weight to 70% by weight: 30% by weight. Contains tin oxide-zinc with a zinc: tin ratio. The protective layer made of tin-zinc oxide having such a mixing ratio is particularly resistant and shows almost no fogging during aging.</p><p num="0021"> In an advantageous embodiment of the refractory glass according to the invention, the protective layer is 0 &lt;z (y + 2x), preferably 0.7 * (y + 2x) z (y + 2x), particularly preferably 0.9 * ( Sn with y + 2x) z (y + 2x)_xZn_yO_zContains. The protective layer made of tin-zinc oxide having such a mixing ratio is particularly resistant and shows almost no fogging during aging. In a particularly advantageous embodiment of the refractory glass according to the invention, the protective layer is ZnSnO.₃Or Zn₂SnO₄Or it contains a mixture of these. The protective layer made of tin-zinc oxide having such a mixing ratio is particularly resistant and shows almost no fogging during aging.</p><p num="0022"> In an advantageous embodiment of the refractory glass according to the invention, the protective layer comprises tin-zinc oxide and any doping material and production-related admixture. The protective layer made of tin-zinc oxide having such a mixing ratio is particularly resistant and shows almost no fogging during aging.</p><p num="0023"> Lamination of mixed tin oxide-zinc is performed, for example, by adding oxygen as a reaction gas during cathode sputtering.</p><p num="0024"> In an advantageous embodiment of the protective layer according to the invention, the layer thickness d of the protective layer is 2 nm to 500 nm, preferably 3 nm to 50 nm, and particularly preferably 5 nm to 30 nm. For double or multi-layer protective layers, this is especially true for the total thickness of the protective layer. The refractory glass containing the protective layer having these layer thicknesses shows almost no fogging especially during aging.</p><p num="0025"> In an advantageous embodiment of the refractory glass according to the invention, the protective layer is implemented as a multi-layer, preferably as a bilayer compound of metal oxides, metal nitrides, and / or metal silicides. Preferably, the protective layer consists of a double layer structure consisting of a metal nitride, in particular silicon nitride, and a metal oxide, in particular one of the above mixed tin oxide zinc or a doped mixed tin oxide-zinc oxide. Such double protective layers have been found to be particularly resistant to alkaline refractory layers and exhibit much less fogging during aging than single protective layers.</p><p num="0026"> According to the study of the present inventors, the double protective layer containing the protective (sub) layer made of metal nitride, particularly silicon nitride, has a second protective (sub) made of metal oxide, particularly tin oxide-zinc. It has been revealed that the layer has the advantage that it can be implemented thinner than a single protective layer made of metal oxide. Nevertheless, such double protective layers are particularly resistant to alkaline refractory layers and show little fogging during aging.</p><p num="0027"> The effects of the present invention are already obtained when the protective (sub) layer made of silicon nitride has a thickness of only a few nanometers, preferably 1 nm to 15 nm, particularly preferably 3 nm to 10 nm.</p><p num="0028"> The synergistic interaction between the silicon nitride layer and the tin-zinc oxide layer allows the reduction of the second protective (sub) layer of tin-zinc oxide, which is simply tin-zinc oxide. Compared with the case of the protective layer consisting of layers, the good resistance to the fireproof layer remains unchanged, and the total thickness of the double protective layer can be selected to be smaller. The reduction in the overall thickness of the protective layer results in improved optical properties of the refractory glass, as well as increased transparency and reduced color deviation. The metal nitride layer, particularly the silicon nitride layer, is very easy and economical to manufacture from the viewpoint of manufacturing technology, and has high light transmission. In particular, the silicon nitride layer is more economical to manufacture than the tin oxide-zinc layer.</p><p num="0029"> In an advantageous embodiment, the protective (sub) layer made of silicon nitride is placed directly on the tin bath side of the float glass, and the protective (sub) layer made of tin-zinc oxide is the protective (sub) layer made of silicon nitride. Placed on top. Naturally, the order of the materials is that the tin-zinc oxide protective (sub) layer is placed directly on the tin bath side of the float glass, and the silicon nitride protective (sub) layer is the tin-zinc oxide protective (sub) layer. ) Can also be modified to be placed on a layer.</p><p num="0030"> The float plate glass according to the present invention is manufactured by the float method. This method is known, for example, from FR 1 378839 A. In the production of float glass, in the continuous production method, paste-like liquid molten glass is continuously supplied from one side on an elongated bath of liquid tin. The molten glass floats on the tin bath and spreads as a uniform glass film. A very smooth surface is formed as a result of the surface tension of tin and liquid glass. At the back edge of the tin bath, the molten glass is cooled and solidified. In the context of the present invention, the side of the float plate glass that floats on the tin bath during manufacturing is referred to as the "tin bath side". The side of the float plate glass opposite to the tin bath side is called the "atmosphere side".</p><p num="0031"> The float glass preferably contains or contains borosilicate glass, aluminosilicate glass, or alkaline earth silicate glass, particularly preferably soda-lime glass, in particular soda-lime glass conforming to standard EN572-1: 2004. Consists of.</p><p num="0032"> Float glass is advantageously heat-strengthened or partially strengthened. The heat-strengthened or partially strengthened float glass has a pretension of preferably 30 MPa to 200 MPa, particularly preferably 70 MPa to 200 MPa. Float glazing thus reinforced or partially reinforced is known, for example, by DE 197 10 289 C1. Heat-strengthened or partially-strengthened float glass sheets are particularly suitable for refractory glass sheets due to their higher stability, and the effect of the protective layer according to the invention is particularly advantageous.</p><p num="0033"> The thickness of the float glass can vary widely and can ideally be adapted to the requirements of the individual case. It is preferred to use flat glass with a standard thickness of 1 mm to 25 mm, preferably 2 mm to 12 mm. The size of the flat glass can vary widely and is determined by the size of use according to the invention.</p><p num="0034"> The float plate glass can have any three-dimensional shape. Preferably, the three-dimensional shape has no shadow zones so that it can be covered, for example, by cathodic sputtering. Preferably, the flat glass is flat or bent slightly or significantly in one or more spatial directions. The float glass can be colorless or colored. The float glass according to the invention can consist of a composite of two or more individual float glass bonded to each other in each case 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 a multi-layer thereof, preferably 0.3 mm. It has a thickness of ~ 0.9 mm.</p><p num="0035"> In an advantageous embodiment of the refractory glass according to the invention, at least one adhesion improving layer or one adhesion lowering layer is arranged between the protective layer and the refractory layer. The adhesion improving layer contains, for example, an organic hydrophilic substance mainly composed of silane, titanate, or zirconate, which is known, for example, by EP 0 001 531 B1 and EP 0 590 978 A1.</p><p num="0036"> Adhesion lowering layers are hydrophobic, for example, fluoroalkylsilanes, perfluoroalkylsilanes, fluoroalkyltrichlorosilanes, fluoroalkylalkoxysilanes, perfluoroalkylalkoxysilanes, fluoroaliphatic silyl ethers, alkylsilanes, and phenylsilanes and silicones. Contains organic functional silane. Such hydrophobic organic functional silanes are known, for example, by DE 19731 416 C1. The alternative adhesion-reducing layer contains a polymer wax, preferably polyethylene-based.</p><p num="0037"> In an advantageous embodiment of the refractory glass according to the invention, at least one other layer that affects the optical properties of the refractory glass is arranged between the tin bath side of the float glass and the protective layer, for example. Such additional layers, for example, increase the transparency of the refractory glass, reduce reflections, or add color to the transmitted light.</p><p num="0038"> The protective layer is advantageously transparent to electromagnetic waves, preferably electromagnetic waves with wavelengths of 300 nm to 1,300 nm, particularly visible light. "Transparency" means that the total transmittance through the float plate glass coated with the protective layer has a transmittance of more than 50%, preferably more than 70%, particularly preferably more than 90%.</p><p num="0039"> The invention further comprises at least one refractory glass according to the invention and one second float glass having an atmosphere side and a tin bath side, wherein the second float glass is a refractory glass via its atmosphere side. Includes a refractory glazing assembly that is planarly coupled to the refractory layer.</p><p num="0040"> An alternative embodiment of the refractory glazing assembly according to the invention includes at least one refractory glass according to the invention and a second float glass having an atmosphere side and a tin bath side, wherein the second float glass is tin. A second protective layer according to the invention is provided on the bath side, and the second float plate glass is planarly bonded to the fireproof layer of the fireproof plate glass via the second protective layer.</p><p num="0041"> In both options, the end seals are arranged to seal the voids between the float plates, and the voids are filled with a refractory layer along the entire circumference of the float plates.</p><p num="0042"> In the advantageous improvement of the refractory glazing assembly according to the invention, the air side of the float glass of the refractory glass is planarly bonded to the second refractory layer, and the second refractory layer is on the air side of the third float glass. It is connected in a plane.</p><p num="0043"> In an alternative improvement of the refractory glazing assembly according to the invention, the air side of the float glass of the refractory glass is planarly coupled to the second refractory layer, with the second refractory layer via another protective layer. It is joined in a plane to the tin bath side of the third float plate glass.</p><p num="0044"> Such triple glazing assemblies exhibit particularly high stability and fire resistance. Of course, it is also possible to produce refractory glass with four or more float glass sheets, in such refractory glass, each refractory layer and the float immediately adjacent to it to prevent fogging of the view due to aging. The protective layer according to the invention is arranged between the plate glass and the tin bath side. Here, "immediately next to" means that there is no flat glass between the tin bath side and the refractory layer.</p><p num="0045"> The present invention further includes a refractory glazing assembly consisting of a first float glass, a first refractory layer, a second refractory glass, a second refractory layer, and a final refractory glass stacking order, wherein each tin is used. The protective layer according to the invention is arranged between the bath side and the refractory layer arranged immediately next to the bath side.</p><p num="0046"> In this improvement of the refractory glazing assembly according to the invention, at least another float glass and another refractory layer are arranged in the stacking order. As a matter of course, another protective layer according to the invention is arranged between each tin bath side of another float plate glass and the refractory layer arranged immediately next to each tin bath side.</p><p num="0047"> To protect the refractory glazing assembly, especially the refractory layer, from heat and UV light, the refractory glazing assembly and especially the outer float glass can further have an additional functional coating with UV and / or infrared reflective action. In addition, multiple refractory glazing assemblies can be constructed by evacuated or gas-filled intermediate spaces.</p><p num="0048"> The present invention includes a method for manufacturing a refractory glazing assembly, in which at least a) one protective layer is applied to the tin bath side of the first float glass and b) the protective layer is provided. The first float glass and the second float glass are heat-strengthened or partially strengthened, and c) the first float glass is formed so that a gap is formed between the tin bath side of the first float glass and the second float glass. The float glass and the second float glass are held at regular intervals from each other, and the narrow side of the gap between the float glass is sealed by the edge seal along the edge of the float glass and all around the edge of the float glass. Then, d) a liquid refractory layer is put into the void and cured.</p><p num="0049"> In an advantageous improvement of the method according to the invention, in the manufacturing process c), a filling port through which a liquid refractory layer can later be injected into the void is removed from the end seal. Then, in the manufacturing process e), the filling port can be sealed by an end seal or other means.</p><p num="0050"> In an advantageous embodiment of the method according to the invention, the third float glass is held at regular intervals from the first or second float glass so that the voids formed thereby are filled by the second refractory layer. , The manufacturing process is repeated. This manufacturing process can be performed in parallel. That is, three or more float glass sheets are held simultaneously at certain intervals, and a refractory layer is formed by simultaneously adding an aqueous solution of silicate or hydrogel. Of course, the method for forming multipane-fire-rated glazing assemblies, including four or more float-plated glazings, can also be repeated in this way.</p><p num="0051"> The coating of the protective layer in the manufacturing step (a) can be carried out by a method known per se, preferably by magnetically assisted cathode sputtering. This is particularly advantageous for the simple, fast, economical and uniform coating of float glass.</p><p num="0052"> A method for producing a mixed tin oxide-zinc layer by reactive cathode sputtering is known, for example, by DE 19848751 C1. Mixed tin oxide-zinc is preferably a target containing 5% to 95% zinc, 5% to 95% tin, and 0% to 10% antimony, as well as manufacturing-related mixtures. Used to deposit. The target particularly preferably contains 15% to 70% by weight zinc, 30% to 85% by weight tin, and 0% to 5% by weight antimony, as well as manufacturing-related admixtures of other metals. .. The deposition of mixed tin oxide-zinc is carried out, for example, by adding oxygen as a reaction gas during cathode sputtering.</p><p num="0053"> Alternatively, the protective layer can be applied by vapor phase deposition, chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), by the sol-gel method, or by the wet chemical method.</p><p num="0054"> In the manufacturing step (b), the first float plate glass and the second float plate glass are held at regular intervals from each other so that voids are formed. This can be done, for example, by a spacer preferably located in the edge region of the float glass. The spacer can remain as a fixed component in the refractory glazing assembly or can be removed. Such spacers advantageously contain or consist of polyisobutylene or another suitable material, in particular plastic. Alternatively, the float glass can be fixed in place by an external holder.</p><p num="0055"> In the manufacturing process (c), a pourable solution of the refractory layer is charged into the voids and cured to form the refractory layer. For example, in the case of a refractory layer consisting of a water-containing alkaline polysilicate, the alkaline silicate is integrated with a curing agent that contains or releases silicon dioxide. The chargeable compound formed from it is charged into the voids. The compound cures there and retains its water content to form a solid polysilicate layer. Methods for producing refractory layers of hydrogels are known, for example, by WO 94/04355 or DE 40 01 677 C1.</p><p num="0056"> The present invention further includes the use of a protective layer according to the invention between the tin bath side of the float glass and a refractory layer, particularly an alkaline refractory layer, to reduce fogging of the float glass due to aging.</p><p num="0057"> The present invention further uses fireproof glass as an architectural element, as a partition, as part of an external facade on land, on the water, or in the air, or as a window in a building or car, or as an internal component in furniture and equipment. including.</p><p num="0058"> The invention further includes the use of heat-reinforced or partially reinforced float glass with a protective layer in the fire-resistant glass or fire-resistant glazing assembly to improve the adhesion between the end seal and the float glass.</p><p num="0059"> The present invention will be described in detail below with reference to the drawings and examples. The drawings are not completely on scale. The present invention is not limited by the drawings.</p>

0060<figref num="1A">It is the schematic sectional drawing of the refractory glass according to the invention.</figref><figref num="1B">It is a schematic plan view of the refractory glass according to the invention of FIG. 1A.</figref><figref num="2A">It is the schematic sectional drawing of the refractory glazing assembly which concerns on invention.</figref><figref num="2B">FIG. 3 is a schematic cross-sectional view of an alternative exemplary embodiment of a refractory glazing assembly according to the invention.</figref><figref num="3">FIG. 3 is a schematic cross-sectional view of an alternative exemplary embodiment of a refractory glazing assembly according to the invention.</figref><figref num="4A">Refractory glazing A according to the invention is a schematic sectional view of an alternative exemplary embodiment of the assembly.</figref><figref num="4B">FIG. 3 is a schematic cross-sectional view of an alternative exemplary embodiment of a refractory glazing assembly according to the invention.</figref><figref num="5">It is a flowchart of an exemplary embodiment of the method according to the invention.</figref><figref num="6">It is a figure of the fogging of the refractory glass according to the invention compared with the prior art.</figref><figref num="7">FIG. 3 is a schematic cross-sectional view of another alternative exemplary embodiment of the refractory glass according to the invention.</figref><figref num="8">FIG. 3 is a schematic cross-sectional view of another alternative exemplary embodiment of the refractory glazing assembly according to the invention.</figref><figref num="9A">It is the schematic of the method for manufacturing the refractory glazing assembly which concerns on invention.</figref><figref num="9B">It is the schematic of the method for manufacturing the refractory glazing assembly which concerns on invention.</figref><figref num="9C">It is the schematic of the method for manufacturing the refractory glazing assembly which concerns on invention.</figref><figref num="9D">It is the schematic of the method for manufacturing the refractory glazing assembly which concerns on invention.</figref>

0061FIG. 1A shows a schematic cross-sectional view of the refractory glass 10 according to the invention. FIG. 1B shows a schematic plan view of the refractory glass 10 in direction III. The refractory glass 10 includes a float glass 1.1 having an atmospheric side I and a tin bath side II. Float plate glass 1.1 has, for example, a thickness b of 5 mm and dimensions of 2 m × 3 m. Of course, the float glass 1.1 has different thicknesses and can also have dimensions suitable for each intended use.

0062The protective layer 3.1 is arranged in a plane on the tin bath side II of the float plate glass 1.1. The float glass 1.1 is heat-strengthened or partially strengthened together with the protective layer 3.1 so that the float glass 1.1 and the protective layer 3.1 are firmly bonded to each other. The refractory layer 3.1 made of alkaline polysilicate is placed on the protective layer 3.1. The protective layer 3.1 extends over a portion, preferably substantially the entire tin bath side II of the float glass 1.1. The protective layer 3.1 extends over the entire surface, in particular, between the refractory layer 2.1 and the float glass 1.1. Therefore, the surface of the tin bath side II of the float plate glass 1.1 can be reliably protected from the alkaline polysilicate of the refractory layer 2.1.

0063Protective layer 3.1 contains, for example, antimony-doped tin-zinc oxide and is deposited by cathodic sputtering. The target for deposition of Protective Layer 3.1 contains 30% by weight zinc, 68% by weight tin, and 2% by weight antimony. The deposition is carried out while adding oxygen as a reaction gas during cathodic sputtering. The thickness d of the protective layer 3.1 is, for example, 25 nm.

0064The refractory layer 2.1 contains, for example, a cured polysilicate, which is formed from an alkaline silicate and at least one curing agent, such as potassium silicate and colloidal silicic acid. In an alternative embodiment, potassium silicate can also be produced directly from the caustic potash solution and silicon dioxide. In polysilicate, the molar ratio of silicon dioxide to potassium oxide (SiO)₂: K₂O) is, for example, 4.7: 1. The refractory layer 2.1 typically has a pH of 12 and is alkaline. The thickness h of the refractory layer 2.1 is, for example, 3 mm.

0065The end seal 6 is arranged on the float plate glass 1.1 so as to surround the refractory layer 2.1 along the end of the float plate glass 1.1. The end seal 6 contains or consists of, for example, a sealant or adhesive mainly composed of polysulfides, polyurethanes, polysilicones, and / or reactive hot melts. The end seal 6 made of polysulfide has been found to be particularly advantageous when combined with the protective layer 3.1 made of tin-zinc oxide, as it has good adhesion and long-term stability. The end seal 6 can be placed directly on the float glass 1.1 having the protective layer 3.1 according to the invention. This is because the protective layer 3.1 is particularly tightly bonded to the float glass 1.1 as a result of being strengthened together.

0066FIG. 2A shows a schematic cross-sectional view of the refractory glazing assembly according to the invention. The refractory glazing assembly 100 according to the invention includes, for example, the refractory glass 10 according to the invention, as shown in FIG. Further, the refractory layer 2.1 of the refractory glass 10 is planarly bonded to the atmosphere side I of the second float glass 1.2 on the opposite side of the protective layer 3.1. The feature of the second float plate glass 1.2 corresponds to, for example, the float plate glass 1.1.

0067Again, the end seal 6 is placed between the float glass 1.1 and 1.2 so as to surround the refractory layer 2.1. The end seal 6 together with the float glass sheets 1.1 and 1.2 forms a hermetically sealed void in which the refractory layer 2.1 is protected from the environment against air and moisture. Spacers 5 can be placed between the float glazings 1.1 and 1.2 to keep the spacing between the float glazings 1.1 and 1.2 constant and stable during manufacturing and use. The spacer 5 is made of, for example, polyisobutylene or other suitable material, especially plastic.

0068FIG. 2B shows a schematic cross-sectional view of an alternative exemplary embodiment of the refractory glazing assembly 100 according to the invention. The refractory glazing assembly 100 according to the invention corresponds to that of FIG. 2A. In order to improve the characteristics at the time of ignition, the adhesive lowering layer 4 is arranged between the protective layer 3.1 and the refractory layer 2.1 and between the refractory layer 2.1 and the second float glass 1.2. The adhesive lowering layer 4 contains, for example, a hydrophobic organic functional silane. The adhesive lowering layer 4 has the advantage that individual fragments of the refractory layer 3.1 can be separated without losing the continuity of the refractory layer 3.1, especially when the float glass plates 1.1 and 1.2 are damaged during ignition. Has.

0069FIG. 3 is a schematic cross-sectional view of an alternative exemplary embodiment of the refractory glazing assembly 100 according to the invention. The refractory glazing assembly 100 according to the invention includes, for example, the refractory glass 10 according to the invention as shown in FIG. Further, the refractory layer 2.1 of the refractory glass 10 is planarly bonded to the tin bath side II of the second float glass 1.2 on the opposite side of the protective layer 3.1 via the second protective layer 3.2. The second float glass 1.2 and the second protective layer 3.2 thus constitute the refractory glass 10.1 according to the invention together with the refractory layer 2.1. Since the tin bath side II of the float plate glass 1.1 and the tin bath side II of the second float plate glass 1.2 are both separated from the refractory layer 2.1 by the protective layers 3.1 and 3.2, they were passed through the refractory glazing assembly 100 due to aging according to the invention. Clouding of visibility is prevented.

0070Such a fireproof glazing assembly 100 is suitable for independent use as a building element in a building or as a glazing assembly in an automobile.

0071FIG. 4A outlines an alternative exemplary embodiment of the refractory glazing assembly 101 according to the invention, using an example of a triple glazing assembly comprising three float glass sheets 1.1, 1.2, 1.3 and two refractory layers 2.1, 2.2. A cross-sectional view is shown. The refractory glazing assembly 101 according to the invention includes, for example, the refractory glass 10 according to the invention as shown in FIG. Further, the refractory layer 2.1 of the refractory glass 10 is planarly bonded to the atmosphere side I of the second float glass 1.2 on the opposite side of the protective layer 3.1. The second float glass 1.2 has a second protective layer 3.2 on its tin bath side II, through which it is bonded to the second refractory layer 2.2. As a result, the second float plate glass 1.2, the protective layer 3.2, and the refractory layer 2.2 constitute the refractory glass II according to the invention. The side of the second refractory layer 2.2 facing away from the second protective layer 3.2 is coupled to the atmospheric side I of the third float glass 1.3.

0072FIG. 4B shows an alternative exemplary embodiment of the refractory glazing assembly 101 according to the invention. The refractory layer 2.1 of the refractory glass 10 according to the present invention is planarly coupled to the atmosphere side I of the second float glass 1.2. Further, the atmospheric side I of the float plate glass 1.1 is planarly bonded to the second refractory layer 2.2. The second refractory layer 2.2 is planarly bonded to the atmosphere side I of the third float plate glass 1.3. This exemplary embodiment has, in particular, the advantage that only one invention of protective layer 3.1 is required to manufacture the aging resistant refractory glazing assembly 101. This is because, due to the preferred configuration of the outer float plate glasses 1.2 and 1.3, only the tin bath side II of the float plate glass 1.1 is placed immediately next to the refractory layer 2.1 without being separated by the glass.

0073The triple glazing assemblies shown in Figures 4A and 4B show particularly high stability and fire resistance. Of course, similarly, in order to prevent fogging of the view due to aging according to the invention, the protective layer according to the invention was arranged between each refractory layer and the tin bath side of the float glass plate arranged immediately next to each refractory layer. It is also possible to manufacture refractory glass including four or more float glass.

0074FIG. 5 shows a flowchart of an exemplary embodiment of the method according to the invention for manufacturing the refractory glazing assembly 100 according to the invention of FIG.

0075FIG. 6 shows a fogging diagram in the aging test of the refractory glass 10 according to the invention, as compared with the refractory glass according to the prior art as a comparative example. In the accelerated aging test, each float glass plate was immersed in an aqueous solution of potassium silicate at a temperature of 80 ° C. for 4 hours. The aqueous potassium silicate solution is the alkaline moiety in the production of the refractory layer according to the invention comprising alkaline polysilicate-hydrogel. Fogging was measured with a "Haze-Guard Plus" type haze meter manufactured by BYK-Gardner Co., Ltd.

0076Example 1 is a float plate glass according to the invention, wherein the tin bath side II is coated with a protective layer made of tin-zinc oxide. The ratio of tin to zinc was 50% by weight: 50% by weight. The thickness d of the protective layer was 25 nm. After the aging test, 0.3% cloudiness was measured.

0077Example 2 is a float plate glass according to the invention, wherein the tin bath side II is coated with a protective layer made of zinc oxide. The thickness d of the protective layer was 25 nm. After the aging test, 0.7% cloudiness was measured.

0078Example 3 is a float plate glass according to the invention, wherein the tin bath side II is coated with a protective layer made of indium tin oxide (ITO). The ratio of indium to tin was 90% by weight: 10% by weight. The thickness d of the protective layer was 25 nm. After the aging test, 0.4% cloudiness was measured.

0079A comparative example according to the prior art was a float plate glass in which neither the atmosphere side I nor the tin bath side II was coated, and both sides were exposed to an aqueous solution of potassium silicate. After the aging test, 8.9% cloudiness was measured in the case of the comparative example.

0080In the aging test shown, the atmospheric side I of the float glass plates of Examples 1 to 3 and Comparative Examples was directly exposed to an aqueous solution of potassium silicate because it was not protected by the protective layer according to the invention. Therefore, it can be concluded that fogging is substantially caused by contact of the tin bath side II with an aqueous solution of potassium silicate.

0081Each of the protective layers according to the invention according to Examples 1 to 3 reduced the fogging of the float plate glass to a value &lt;1% as compared with the comparative example according to the prior art which did not include the protective layer 3 according to the invention. In the case of the protective layer according to the invention made of tin oxide-zinc according to Example 1, the fogging was actually reduced to 1/89. This result was unpredictable and surprising to those skilled in the art.

0082FIG. 7 shows a schematic cross-sectional view of an alternative exemplary embodiment of the refractory glass 10 according to the invention. Float plate glass 1.1 and refractory layer 2.1 are implemented according to FIG. Protective layer 3.1 is implemented as a bilayer structure composed of a first protective (sub) layer 3.1a and a second protective (sub) layer 3.1b. The protective (sub) layer 3.1a has a thickness d of, for example, 8 nm, for example, a silicon nitride layer, in particular Si.₃N₄Consists of. The protective (sub) layer 3.1b has, for example, a thickness db of 15 nm and consists of, for example, a tin oxide-zinc layer, as shown in FIG. Therefore, the overall thickness d of the protective layer 3.1 was 23 nm.

0083As revealed by our studies, it is already possible to obtain an advantageously increased aging resistance and a significantly reduced fogging by the protective (sub) layer 3.1a made of silicon nitride with a thickness d of 3 nm. there were. At the same time, it was possible to reduce the thickness of the tin-zinc oxide layer without degrading aging resistance or fogging.

0084In this exemplary embodiment, the protective (sub) layer 3.1a made of silicon nitride is placed directly on the tin bath side II of the float glass 1.1 and the protective (sub) layer 3.1b made of tin oxide-zinc oxide is made of silicon nitride. It is located on the protective (sub) layer 3.1a. Naturally, the order of the materials should be changed so that the tin-zinc oxide layer is placed directly on the tin bath side of the float glass and the silicon nitride layer is placed on the tin-zinc oxide layer. You can also.

0085FIG. 8 shows another alternative exemplary embodiment of the refractory glazing assembly 101 according to the invention. The refractory glazing assembly 101 of FIG. 8 corresponds to the refractory glazing assembly 101 of FIG. 4b, where only the protective layer 3.1 of FIG. 4b is a dual layer consisting of a protective (sub) layer 3.1a and a protective (sub) layer 3.1b. It is implemented as a structure. The protective (sub) layers 3.1a and 3.1b correspond to, for example, the layer in Figure 7.

0086Table 1 summarizes the results of the aging and fogging tests for various exemplary embodiments of the refractory glass 10 according to the invention.

0087<tables num="1"><img id="000003" he="85" wi="165" file="JP2016506352A_D0001.tif" img-format="tif" img-content="drawing" /></tables>

0088The first column shows the material of the protective layer 3.1 and the second column shows the thickness. The protective layer 3.1 is placed directly on the float glass 1.1 in each case. The description silicon nitride (3.1a) / tin oxide-zinc (3.1b) indicates that the protective layer 3.1 consists of a bilayer structure. The first protective (sub) layer 3.1a made of silicon nitride is placed directly on the float glass 1.1 and the second protective (sub) layer 3.1b made of tin oxide-zinc oxide is the first protective. It is placed directly on the (sub) layer 3.1a. For the tin-zinc oxide (3.1a) / silicon nitride (3.1b) layer order, the reverse order also applies.

0089Surprisingly, silicon nitride (3.1a) has a layer thickness of 3 nm for the first protective (sub) layer 3.1a and a layer thickness of 15 nm for the second protective (sub) layer 3.1b. ) / Tin oxide-zinc (3.1b) layer order is similar as single protective layer 3.1 consisting of tin oxide-zinc at 25 nm, even though the overall thickness could be reduced to 25 nm-18 nm. Showed good aging resistance and less fogging. For a combination of 8 nm layer thickness of silicon nitride and 15 nm layer thickness of tin oxide-zinc, in fact, more aging resistance and less fogging than a single protective layer 3.1 of tin oxide-zinc of 25 nm. Was clarified by experiments.

0090As revealed by the diligent studies of the inventors, the combination of a layer made of a metal nitride such as silicon nitride and a layer made of a metal oxide such as zinc oxide-tin produces an aging-resistant refractory glazing assembly. However, it is particularly advantageous for preventing fogging in the case of contact with the alkaline refractory layer on the tin bath side of the float plate glass.

00919A-D show a schematic sequence of exemplary embodiments for manufacturing the refractory layer 100 according to the invention using four manufacturing steps. As shown in FIG. 9A, in the first manufacturing step, the protective layer 3.1 is applied to the tin bath side II of the float plate glass 1.1 by, for example, cathode sputtering. In another manufacturing process, the float glass 1.1 on which the protective layer 3.1 is placed is heat-enhanced or partially strengthened, for example, by shared heating of the surface and quenching by a cold air stream. The float plate glass 1.1 treated in this way is shown in FIG. 9B. A tight junction is formed between the float glass 1.1 and the protective layer 3.1 by shared thermal or partial reinforcement.

0092In the manufacturing process shown in FIG. 9C, heat-strengthened or partially-strengthened float glass 1.1 and another float glass 1.2 are positioned at regular intervals from each other. The float plate glass 1.2 is turned over so that its atmospheric side I, that is, the protective layer 3.1 is directed toward the tin bath side II of the float plate glass 1.1. Of course, the float plate glass 1.2 may have a heat-strengthened or partially strengthened protective layer on the tin bath side II together with the float plate glass 2.1 after coating.

0093The float glazings 1.1 and 1.2 are held at a constant distance from each other by an external device (not shown) such that voids 8 are formed between the float glazings 1.1 and 1.2, and the spacing is that of the next refractory layer. Prescribe the thickness. Further fixation is preferably carried out by one or more spacers 5. The spacer 5 preferably extends along the entire circumference of the float glass plates 1.1 and 1.2, for example, leaving only the filling port 7 on the narrow side above the void 8 open. In addition, the narrow side of the gap 8 between the float glass 1.1 and 1.2 is sealed by the end seal 6. The end seal 6 is made of a sealant such as polysulfide. The end seal 6 is arranged all around the void 8 except for the area of the filling port 7.

0094In the manufacturing process shown in FIG. 9D, the still liquid refractory layer 2.1 is introduced into the void 8 through the filling port 7. The refractory layer 2.1 consists of, for example, an alkaline silicate in the form of potassium silicate and colloidal silicic acid, eg, 4.7: 1 SiO.₂And K₂It is prepared as an inputtable compound that cures to form a polysilicate having a molar ratio to O. The compound that can be charged is degassed by a known method and charged into the void 8. The compound is sufficiently fluid to drive away the air present in the void 8 and not to form any gas-filled sites. After the void 8 is completely filled, the filling port 7 is sealed by the end seal 6. Therefore, the refractory layer 2.1 is hermetically sealed from the environment. The refractory glazing assembly 100 thus manufactured is stored in place until the reaction process in the refractory layer 2.1 is completed and the polysilicate is cured.

0095Table 2 summarizes the results of aging tests on various exemplary embodiments of the refractory glazing assembly 100 according to the present invention. The examples shown correspond to the exemplary embodiments of FIG. 2A, except for the differences identified.

0096<tables num="2"><img id="000004" he="69" wi="170" file="JP2016506352A_D0001.tif" img-format="tif" img-content="drawing" /></tables>

0097The refractory glazing assembly according to the invention of Example B included a float plate glass 1.1 and a protective layer 3.1 made of tin-zinc oxide on the tin bath side II of the float plate glass 1.1. Both the float glass 1.1 and the protective layer 3.1 were heat strengthened. This means that the protective layer 3.1 was first deposited on the tin bath side II of the float plate glass 1.1, and then the coated float plate glass 1.1 was heat strengthened.

0098On the contrary, in the case of the refractory glass according to Example A, the float glass 1.1 was first heat-strengthened, and then the protective layer 3.1 made of tin oxide-zinc oxide was applied to the tin bath side II of the float glass 1.1.

0099Both refractory glazing assemblies showed little cloudiness during aging. The protective layer 3.1 made of tin oxide-zinc was able to protect the tin bath side II of the float plate glass 1.1 from the corrosion of the alkaline refractory layer 2.1 in each case.

0100However, in the aging test, a large difference appeared in the area of the end seal. In Example A, defects in the adhesiveness and seal sealability of the end seal were observed. Therefore, air could penetrate inside the refractory glazing assembly and moisture could leak out of the refractory compound and damage the refractory glazing assembly. Such refractory glazing assemblies are not very useful. As a result, such protective layers in the area of the end seal need to be removed with considerable effort prior to application of the end seal, for example by mechanical grinding or chemical etching.

0101In the case of Example B, the adhesiveness of the end seal and the seal sealability were greatly improved. The adhesiveness of the end seals on the protective layer 3.1 of the float glass 1.1, both reinforced, was stable and did not lose its bond to the float glass 1.1 even after multiple aging cycles. This is because the float glass 1.1 and the protective layer 3.1 are both heat-strengthened or partially strengthened to form a stable bond between the end seal 6 and the float glass 1.1 to prevent the protective layer 3.1 from peeling or melting. Can be explained by Complex removal of protective layer 3.1 in the area of the end seal is not required.

0102This result was unpredictable and surprising to those skilled in the art.

01031, 1.1, 1.2, 1.3 Float plate glass 2, 2.1, 2.2 refractory layer 3, 3.1, 3.2, 3.3 Protective layer 3.1a, 3.1b Protective (sub) layer, protective layer, layer 4 Adhesion lowering layer 5 spacer 6 End seal 7 Filling port 8 voids 10, 10.1, 11 refractory glass 100, 101 refractory glazing assembly I Float plate glass atmospheric side II Float plate glass tin bath side III Direction of plan view on float glass b Float plate glass thickness d, d_a, D_b Protective layer thickness h Thickness of refractory layer