FIRE PROTECTION PANE AND FIRE PROTECTION GLAZING

Abstract

A fire-protection pane, including at least one float glass pane with an atmosphere side and with a tin bath side, at least one protective layer, which is arranged in a surfaced manner on the atmosphere side and/or the tin bath side, and at least one fire-protection layer, which is arranged in a surfaced manner on the protective layer. The protective layer is a multi-layer layer structure and includes a first sub-protective-layer of metal-doped silicon nitride, and a second sub-protective-layer of a tin/zinc oxide or a doped tin/zinc oxide.

Claims

1. A fire-protection pane, comprising at least one float glass pane with an atmosphere side and with a tin bath side, at least one protective layer that is arranged in a surfaced manner on the atmosphere side and/or the tin bath side and at least one fire-protection layer, that is arranged in a surfaced manner on the protective layer, wherein the protective layer is a multi-layer layer structure and comprises or contains a first sub-protective-layer of metal-doped silicon nitride, and a second sub-protective-layer of a tin/zinc oxide or a doped tin/zinc oxide.

2. The fire-protection pane according to claim 1, wherein the protective layer is a two-layer layer structure.

3. The fire-protection pane according to claim 1, wherein the first sub-protective-layer is arranged directly on the float glass pane, and the second sub-protective-layer is arranged between the first sub-protective-layer and the fire-protection layer.

4. The fire-protection pane according to claim 1, wherein the protective layer is arranged in a surfaced manner only on the tin bath side of the float glass pane.

5. The fire-protection pane according to claim 1, wherein the fire-protection layer is alkaline.

6. The fire-protection pane according to claim 1, wherein the fire-protection layer comprises alkali silicate, alkali silicate water glass, alkali phosphate, alkali tungstenate, alkali molybdate and/or mixtures or layer compositions thereof, preferably alkali polysilicate, alkali polyphosphate, alkali polytungstenate, alkali polymolybdate and/or mixtures or layer compositions thereof, and wherein the alkali element is preferably sodium, potassium, lithium and/or mixtures thereof, or the fire-protection layer comprises a hydrogel of crosslinked monomers and/or polymers, preferably polyacrylamide, poly-N-methyl acrylamide or polymerised 2-hydroxy-3-methacryloxypropyl trimethyl ammonium chloride.

7. The fire-protection pane according to claim 1, wherein the share of the doping metal of the first sub-protective-layer is 1% by weight to 20% by weight, and preferably from 3% by weight to 7% by weight and/or the doping metal of the first sub-protective-layer is aluminum.

8. The fire-protection pane according to claim 1, wherein the first sub-protective-layer has a thickness da of 5 nm to 50 nm and preferably of 8 nm to 13 nm.

9. The fire-protection pane according to claim 1, wherein in the second sub-protective-layer, the ratio of zinc:tin is 5% by weight:95% by weight to 95% by weight:5% by weight and preferably from 15% by weight:85% by weight to 70% by weight:30% by weight.

10. The fire-protection pane according to claim 1, wherein the second sub-protective-layer comprises at least one doping element, preferably antimony, fluorine, boron, silver, ruthenium, palladium, aluminum and tantalum, and the share of the doping element of the second sub-protective-layer is from 0.1% by weight to 5% by weight and preferably from 0.5% by weight to 2.5% by weight.

11. The fire-protection pane according to claim 1, wherein the second sub-protective-layer has a thickness db of 10 nm to 50 nm and preferably from 13 nm to 21 nm.

12. The fire-protection pane according to claim 1, wherein the float glass pane comprises borosilicate glass, alumosilicate glass, alkaline earth silicate glass or soda lime glass and preferably soda lime glass according to EN 572-1:2004 and/or the float glass pane is thermally prestressed or part-prestressed, and/or the float glass pane has a thickness b of 1 mm to 25 mm and preferably of 2 mm to 12 mm and/or the fire-protection layer has a thickness h of 0.5 mm to 70 mm.

13. A fire-protection glazing, comprising: a fire-protection pane according to claim 1 and a float glass pane with an atmosphere side and with a tin bath side, wherein the atmosphere side or the tin bath side via a protective layer is connected in a surfaced manner to the fire-protection layer of the fire-protection pane.

14. The fire-protection glazing according to claim 13, wherein the atmosphere side of the float glass pane of the fire-protection pane is connected in a surfaced manner to a fire-protection layer, and the fire-protection layer is connected in a surfaced manner to the atmosphere side or via a further protective layer to the tin bath side of a third float glass pane.

15. The fire-protection glazing according to claim 13, wherein the float glass pane or the float glass pane is connected in a surfaced manner to at least one stack sequence of a further fire-protection layer and of a further float glass pane, wherein a further protective layer according to the invention is arranged between each tin bath side and a directly adjacently arranged fire-protection layer.

16. A method for manufacturing a fire-protection glazing, wherein at least a. one protective layer is deposited on the tin bath side of a float glass pane, b. the float glass pane and a second float glass pane are thermally prestressed or part-prestressed, c. the float glass pane and the second float glass pane are held at a fixed distance, so that a mould cavity is formed between the tin bath side of the float glass pane and the second float glass pane and d. a fire-protection layer is cast into the mould cavity and cured.

17. The method according to claim 16, wherein the method steps are repeated at least once with a further float glass pane and with a further fire-protection layer.

18. Use of a protective layer between a tin bath side of a float glass pane and a fire-protection layer according to claim 1, for reducing the hazing of a float glass pane on ageing.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0070] The invention is hereinafter explained in more detail by way of drawings and an example. The drawings are not completely true to scale. The invention is in no way limited by the drawings. There are shown in:

[0071] FIG. 1: a schematic cross-sectional representation of a fire-protection pane according to the invention,

[0072] FIG. 2A: a schematic cross-sectional representation of a fire-protection glazing according to the invention,

[0073] FIG. 2B: a schematic cross-sectional representation of an alternative embodiment of a fire-protection glazing according to the invention,

[0074] FIG. 3: a schematic cross-sectional representation of an alternative embodiment of a fire-protection glazing according to the invention,

[0075] FIG. 4A: a schematic cross-sectional representation of an alternative embodiment of a fire-protection glazing according to the invention,

[0076] FIG. 4B: a schematic cross sectional representation of an alternative embodiment of a fire-protection glazing according to the invention,

[0077] FIG. 5: a flow diagram of one embodiment example of the method according to the invention and

[0078] FIG. 6: a diagram of the hazing of fire-protection panes with different protective layers.

DETAILED DESCRIPTION OF THE INVENTION

[0079] FIG. 1 shows a schematic representation of a fire-protection pane 10 according to the invention, in cross section. The fire-protection pane 10 includes a float glass pane 1.1 with an atmosphere side I and with a tin bath side II. The float glass pane 1.1, for example, has a thickness b of 5 mm and dimensions of 2 m3 m. It is to be understood that the float glass pane 1.1 can also have other thicknesses and dimensions adapted to the respective application purpose.

[0080] A protective layer 3.1 is arranged on the tin bath side II of the float glass pane 1.1. A fire-protection layer 3.1 of an alkaline polysilicate is arranged on the protective layer 3.1. The protective layer 3.1 extends partly and preferably essentially over the entire tin bath side II of the float glass pane 1.1. The protective layer 3.1 in particular extends over the complete surface between the fire-protection layer 2.1 and the float glass pane 1.1. By way of this, it is ensured that the surface of the tin bath side II of the float glass pane 1.1 is protected from the alkaline polysilicate of the fire-protection layer 2.1.

[0081] The protective layer 3.1 is designed as a two-layer layer structure of a first sub-protective-layer 3.1a and of a second sub-protective-layer 3.1b.

[0082] The first sub-protective-layer 3.1a, for example, consists of an aluminium-doped silicon nitride layer and was deposited by way of cathode spluttering. The deposition was effected from a target of aluminium-doped silicon amid the addition of nitrogen as a reaction gas during the cathode spluttering. The aluminium-doped silicon nitride layer, for example, has a share of the doping metal of 5% by weight and a thickness d.sub.a of 8 nm, for example.

[0083] The second sub-protective-layer 3.1b of antimony-doped tin/zinc oxide was deposited by way of cathode spluttering. The target for deposition of the second sub-protective-layer 3.1b contained 68% by weight of zinc, 30% by weight of tin and 2% by weight of antimony. The deposition was effected amid the addition of oxygen as a reaction gas during the cathode spluttering. The second sub-protective-layer 3.1b has a thickness d.sub.b, for example, of 15 nm. The thickness d of the complete protective layer 3.1 is thus 23 nm.

[0084] As trials of the inventor have shown, an advantageously increased ageing resistance and a greatly reduced hazing as well as an increased durability in the corrosion test and in the scratch test could be achieved already with a sub-protective-layer 3.1a of aluminium-doped silicon nitride, which had a thickness d.sub.a of 3 nm.

[0085] In this design example, the sub-protective-layer 3.1a of aluminium-doped silicon nitride is arranged directly on the tin bath side II of the float glass pane 1.1, and the second sub-protective-layer 3.1b of antimony-doped tin/zinc oxide is arranged on the first sub-protective-layer 3.1a of aluminium-doped silicon nitride. It is to be understood that the sequence of materials can also be exchanged, so that a layer of antimony-doped tin/zinc oxide is arranged directly on the tin bath side of the float glass pane, and a layer of aluminium-doped silicon nitride is arranged on the layer of antimony-doped tin/zinc oxide.

[0086] The fire-protection layer 2.1 for example includes a cured polysilicate, which is formed from an alkali silicate and at least one curing agent, for example of potassium silicate or colloidal silicic acid. In an alternative design, the potassium silicate can also be manufactured directly from potassium hydroxide solution and silicon dioxide. The molar ratio of silicon dioxide and potassium oxide (SiO.sub.2:K.sub.2O), for example, is 4.7:1. Such a fire-protection layer 2.1 is typically alkaline with a pH value of 12. The thickness h of the fire-protective layer 2.1 is 3 mm, for example.

[0087] FIG. 2A shows a schematic cross-sectional representation of a fire-protection glazing 100 according to the invention. The fire-protection glazing 100 according to the invention, for example, includes a fire-protection pane 10 according to the invention, as is described in FIG. 1. Furthermore, the fire-protection layer 2.1 of the fire protection pane 10 is connected to the atmosphere side I of a second float glass pane 1.2 in a surfaced manner at the side of fire-protection layer, which is opposite to the protective layer 3.1. The second float glass pane 1.2 in its nature corresponds, for example, to the float glass pane 1.1.

[0088] FIG. 2B shows a schematic cross-sectional representation of an alternative example of a fire-protection glazing 100 according to the invention. The fire-protection glazing 100 according to the invention corresponds to that of FIG. 2A. A bonding reduction layer 4 is arranged 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 float glass pane 1.2, in order to improve the characteristics in the case of fire. The bonding reduction layer 4, for example, includes organofunctional silane with a hydrophobic effect. The bonding reduction layer 4 has the particular advantage that in the case of fire, with the fracturing of the float glass pane 1.1, 1.2, the individual fragments can detach from the fire-protection layer 3.1 without the coherency of the fire-protection layer 3.1 being lost.

[0089] FIG. 3 shows a schematic cross-sectional representation of an alternative example of a fire-protection glazing 100 according to the invention. The fire-protection glazing 100 according to the invention, for example, includes a fire-protection pane 10 according to the invention, as is described in FIG. 1. The fire-protection layer 2.1 of the fire-protection pane 10 at the side that is opposite to the protective layer 3.1 is moreover connected via a second protective layer 3.2 to the tin bath side II of a second float glass pane 1.2. Again, the second float glass pane 1.2 and the second protective layer 3.2 with the fire-protection layer 2.1 form a fire-protection pane 10.1 according to the invention. According to the invention, a hazing of the view through the fire-protection glazing 100 is avoided on ageing since the tin bath side II of the float glass pane 1.1 as well as the tin bath side II of the second float glass pane 1.2 are separated from the fire-protection layer 2.1 by a protective layer 3.1, 3.2.

[0090] The first protective layer 3.1 as well as the second protective layer 3.2 consist of two-layer layer structures, wherein a first sub-protective-layer 3.1a, 3.2a, for example, contains aluminium-doped silicon nitride and is arranged directly on the tin bath side II of the float glass panes 1.1, 1.2 in each case, and a second sub-protective-layer 3.1b, 3.2b, for example, of antimony-doped tin/zinc oxide is arranged between the first sub-protective-layers 3.1a, 3.2a and the fire-protection layer 2.1.

[0091] Such a fire-protection glazing 100 is suitable for an independent application as a construction element in a building or as a vehicle glazing.

[0092] FIG. 4A shows a schematic cross-sectional representation of an alternative example of a fire-protection glazing 101 according to the invention, with the example of a 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 for example includes a fire-protection pane 10 according to the invention, as is described in FIG. 1, with a two-layer protective layer 3.1 of a first sub-protective-layer and a second sub-protective-layer. Moreover, the fire-protection layer 2.1 of the fire-protection pane 10 at the side that is opposite to the protective layer 3.1 is connected in a surfaced manner to the atmosphere side I of a second float glass pane 1.2. The second float glass pane 1.2 at its tin bath side II includes a second protective layer 3.2 and is connected via this to a second fire-protection layer 2.2. The second float glass pane 1.2, the protective layer 3.2 and the fire-protection layer 2.2 again form a fire-protection pane 11 according to the invention. The side of the second fire-protection layer 2.2, which is away from the second protective layer 3.2 is connected to the atmosphere side I of a third float glass pane 1.3.

[0093] FIG. 4B shows an alternative embodiment example of a fire-protection glazing 101 according to the invention. The fire-protection layer 2.1 of a fire-protection pane 10 according to the invention is connected in a surfaced manner to the atmosphere side I of a second float glass pane 1.2. The atmosphere side I of the float glass pane 1.1 is moreover connected in a surfaced manner to a second fire-protection layer 2.2. The second fire-protection layer 2.2 is connected in a surfaced manner to the atmosphere side I of a third float glass pane 1.3. This embodiment has the particular advantage that only one protective layer 3.1 according to the invention is required, in order to create a fire-protection glazing 101 that is resistant to ageing, since only the tin bath side II of the float glass pane 1.1 is arranged directly adjacently to the fire-protection layer 2.1 and without a separation by glass, due to a suitable arrangement of the outer-lying float glass panes 1.2, 1.3.

[0094] The triple glazing, which is represented in FIGS. 4A and 4B, displays a particularly high stability and fire-protection effect. It is to be understood that fire-protection panes with four or more float glass panes can also be manufactured according to a similar principle, wherein a protective layer according to the invention is arranged between each fire-protection layer and the directly adjacently arranged tin bath side of a float glass pane, for the inventive avoidance of hazing of the through-view on ageing.

[0095] The fire-protection pane 10, 11 and the fire-protection glazing 100, 101 of the embodiments represented here can include further spacers between the adjacent float glass panes 1.1, 1.2, 1.3 and edge sealing around the fire-protection layers 2.1, 2.2, the spacers being known per se and not being represented here. Suitable materials for the edge sealing, for example, contain polyisobutylene as spacers, and polysulphide, polyurethane or silicone as an edge sealing.

[0096] FIG. 5 shows a flow diagram of one embodiment of the method according to the invention, for manufacturing a fire-protection glazing 100 according to the invention and according to FIG. 2.

[0097] FIG. 6 shows a diagram of the hazing in an ageing test of fire-protection panes 10 with different protective layers of individual layers. The respective float glass pane in the accelerated ageing test was immersed in an aqueous solution of potassium silicate over a time period of 4 hours and at a temperature of 80 C. The aqueous potassium silicate solution is the alkaline component on manufacturing a fire-protection layer according to the invention from an alkali polysilicate hydrogel. The haze was measured with a haze measurement apparatus of the type haze-gard plus of the company BYK Gardner.

[0098] Example 1 is a float glass pane, whose tin bath side II was coated with a protective layer of a single tin/zinc oxide layer. Thereby, the ratio of tin to zinc was 50% by weight:50% by weight. The thickness d of the protective layer was 25 nm. A hazing of 0.3% was measured according to the ageing test.

[0099] Example 2 is a float glass pane, whose tin bath side II was coated with a protective layer of a single zinc oxide layer. The thickness d of the protective layer was 25 nm. A hazing of 0.7% was measured according to the ageing test.

[0100] Example 3 is a float glass pane, whose tin bath side II was coated with a protective layer of a single indium tin oxide (ITO) layer. Thereby, the ratio of indium to tin was 90% by weight:10% by weight. The thickness d of the protective layer was 25 nm. A hazing of 0.4% was measured according to the ageing test.

[0101] The comparative example was a float glass pane, with which neither the atmosphere side I nor the tin bath side II were coated, and thus both sides were exposed to the aqueous solution of potassium silicate. A haze of 8.9% was measured with the comparative example according to the ageing test.

[0102] With the represented ageing tests, the atmosphere sides I of the float glass panes of the Examples 1 to 3 and of the comparative example were not protected by a protective layer and thus were directly exposed to the aqueous solution of potassium silicate. From this, one can conclude that the hazing is effected essentially by the contact of the tin bath side II with the aqueous solution of potassium silicate.

[0103] Each of the protective layers of the Examples 1 to 3 reduces the hazing of the float glass pane to values <1%, in comparison to the comparative example without a protective layer. The haze was even reduced by 89-fold with the protective layer of a single tin/zinc oxide layer according to Example 1. This result was unexpected and surprising to the person skilled in the art.

[0104] Even better results can be achieved for the inventive fire-protection panes 10 with protective layers 3.1 with a two-layer or multi-layer layer structure.

[0105] The results of the ageing test and the haze test for different embodiment examples of fire-protection panes 10 according to the invention with comparative examples are represented in a conclusive manner in Table 1.

TABLE-US-00001 TABLE 1 pane or layer layer structure thickness(es) corrosion test hazing test scratch rest float glass pane/ 4 mm/ good good many Sb:tin/zinc oxide 15 nm float glass pane/ 4 mm/ good satisfactory few Al:silicon nitride 8 nm float glass pane(1.1)/ 4 mm(1.1)/ satisfactory good few Sb:tin/zinc oxide(3.1b)/ 15 nm(3.1b)/ Al:silicon nitride (3.1a) 8 nm(3.1a) float glass pane/ 4 mm/ good very good few B:silicon nitride/ 8 nm/ Sb:tin/zinc oxide 15 nm float glass pane(1.1)/ 4 mm(1.1)/ very good very good almost none Al:silicon nitride (3.1a)/ 8 nm (3.1a)/ Sb:tin/zinc oxide (3.1b) 15 nm (3.1b)

[0106] A fire-protection glazing was examined regarding the corrosion test, the scratch test and the haze test. A fire-protection pane 10 of a float glass pane 1.1 with a protective layer 3.1 on the tin bath side II and of an alkaline fire-protection layer 2.1 was connected to the atmosphere side I of a further float glass pane 1.2, for the manufacture of the fire-protection glazing.

[0107] The respective fire-protection glazing was stored over a time period of 14 days at a temperature of 80 C. in the corrosion test and in the scratch test. The fire-protection glazing in the corrosion test was subsequently visually examined with regard to strip-like hazing, wherein the strips are orientated in the production direction of the float glass pane. Such strip-like hazing is due to an interaction of the fire-protection layer with the tin bath side II of the float glass 1.1. Very good means that almost no strip-like hazing in the production direction is to be recognised and satisfactory means that comparatively much strip-like hazing is to be recognised.

[0108] The fire-protection glazing was moreover visually examined with regard to randomly oriented scratches in the scratch test. Such scratches, inherently of production, result on the tin bath side II of the float glass pane 1.1. Very good means that almost no randomly orientated scratches are to be recognised, and satisfactory means that comparatively many randomly orientated scratches are to be recognised.

[0109] The respective fire-protection glazing was stored over a period of 1 year at a temperature of 60 C. in the haze test. The haze was measured with a haze measurement apparatus of the type haze-gard plus of the company BYK Gardner and indicates the homogeneous hazing of the fire-protection glazing. Very good here means a very slight hazing and satisfactory a greater hazing.

[0110] The material of the protective layer is specified in the first column of Table 1, and its (layer) thickness in the second columns. The protective layers are each arranged directly adjacently to the tin bath side II of the float glass pane 1.1. The detail Al:silicon nitride (3.1a)/Sb:tin/zinc oxide (3.1b) describes a protective layer 3.1 according to the invention and for example specifies that the protective layer 3.1 consists of a two-layer layer structure. Thereby, the firstly mentioned first sub-protective-layer 3.1a of aluminium-doped silicon nitride is arranged directly on the float glass pane 1.1, and the second sub-protective-layer 3.1b of antimony-doped tin/zinc oxide is arranged between the first sub-protective-layer 3.1b and the fire-protection layer 2.1. The reverse sequence accordingly applies to the layer sequence Sb:tin/zinc oxide(3.1b)/Al:silicon nitride (3.1a) according to the invention.

[0111] The tendencies that are represented in the table can be understood within the framework of a surprising model: A single antimony-doped tin/zinc oxide layer acts as a protective layer of the tin bath side II of the float glass pane 1.1 and effectively protects this form alkaline attack of the fire-protection layer 2.1. This leads to good results in the corrosion test and only to a very low hazing in the haze test. A multitude of randomly orientated scratches, which in the scratch test compromise the appearance of the fire-protection glazing, occurs during the production due to the fact that the antimony-doped tin/zinc oxide is relatively soft.

[0112] A single, relatively hard aluminium-doped silicon nitride layer in the corrosion test likewise leads to good results and to less strip-like hazing. A single aluminium-doped silicon nitride layer however only has a satisfactory protective effect in the long-term haze test.

[0113] An inventive protective layer 3.1 of a second sub-protective-layer 3.1b of antinomy-doped tin/zinc oxide directly on the tin bath side II of the float glass pane 1.1 and of a first sub-protective-layer 3.1a of aluminium-doped silicon nitride between the second sub-protective-layer 3.1b and the fire-protection layer 2.1 displays good results in the haze test and in the scratch test, but only satisfactory results in the corrosion test.

[0114] A protective layer 3.1 of a first sub-protective-layer 3.1a of boron-doped silicon nitride directly on the tin bath side II of the float glass pane 1.1 and of a second sub-protective-layer 3.1b of antimony-doped tin/zinc oxide between a first sub-protective-layer 3.1a and the fire-protection layer 2.1 shows very good results in the haze test and less scratches in the scratch test. However, much strip-like hazing can be ascertained in the corrosion test.

[0115] Surprisingly, the best results are provided by way of inventive protective layers 3.1 of a first sub-protective-layer 3.1a of aluminium-doped silicon nitride directly on the tin bath side II of the float glass pane 1.1 and of a second sub-protective-layer 3.1b of antimony-doped tin/zinc oxide between a first sub-protective-layer 3.1a and a fire-protection layer 2.1. These protective layers 3.1 displayed the best results in all three tests.

[0116] Thereby, what is particularly noticeable is the fact that a first sub-protective-layer 3.1a according to the invention and of aluminium-doped silicon nitride in combination with the second sub-protective-layer 3.1 of antimony-doped tin/zinc oxide displayed significantly improved results in the corrosion test as well as in the scratch test, compared to a first sub-protective-layer of boron-doped silicon nitride. This can be explained by the greater hardness of metal-doped silicon nitride layers 3.1a and here in particular of aluminium-doped silicon nitride layers 3.1a in comparison to non-metal-doped silicon nitride layers and here in particular to boron-doped silicon nitride layers. The harder metal-doped silicon nitride layers 3.1a in combination with the second sub-protective-layers 3.1b of antimony-doped tin/zinc oxide displayed the best results in all three tests.

[0117] This result was unexpected and surprising for the man skilled in the art.

LIST OF REFERENCE NUMERALS

[0118] 1, 1.1, 1.2, 1.3 float glass pane [0119] 2.1, 2.2 fire-protection layer [0120] 3.1, 3.2, 3.3 protective layer [0121] 3.1, 3.2a first sub-protective-layer [0122] 3.1b, 3.2b second sub-protective-layer [0123] 4 adhesion reduction layer [0124] 10, 10.1, 11 fire-protection pane [0125] 100, 101 fire-protection glazing [0126] I atmosphere side of a float glass pane [0127] II tin bath side of a float glass pane [0128] b thickness of a float glass pane [0129] d, d.sub.a, d.sub.b thickness of a protective layer [0130] h thickness of a fire-protection layer