Fire-resistant pane and fire-resistant glazing assembly
09937684 · 2018-04-10
Assignee
Inventors
Cpc classification
B32B17/10311
PERFORMING OPERATIONS; TRANSPORTING
C03C17/3405
CHEMISTRY; METALLURGY
B32B2255/28
PERFORMING OPERATIONS; TRANSPORTING
B32B17/10036
PERFORMING OPERATIONS; TRANSPORTING
B32B17/10688
PERFORMING OPERATIONS; TRANSPORTING
B32B17/10165
PERFORMING OPERATIONS; TRANSPORTING
C03C17/3494
CHEMISTRY; METALLURGY
Y10T428/23
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B32B2307/3065
PERFORMING OPERATIONS; TRANSPORTING
Y10T428/24967
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B32B17/10045
PERFORMING OPERATIONS; TRANSPORTING
B32B37/144
PERFORMING OPERATIONS; TRANSPORTING
B32B17/10211
PERFORMING OPERATIONS; TRANSPORTING
B32B17/10174
PERFORMING OPERATIONS; TRANSPORTING
Y10T428/265
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B32B7/14
PERFORMING OPERATIONS; TRANSPORTING
B32B2605/006
PERFORMING OPERATIONS; TRANSPORTING
C03C17/008
CHEMISTRY; METALLURGY
B32B37/18
PERFORMING OPERATIONS; TRANSPORTING
C03C21/005
CHEMISTRY; METALLURGY
Y10T428/266
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C03C17/42
CHEMISTRY; METALLURGY
B32B17/10788
PERFORMING OPERATIONS; TRANSPORTING
C03C17/3435
CHEMISTRY; METALLURGY
International classification
G05B19/18
PHYSICS
C03C17/00
CHEMISTRY; METALLURGY
C03C21/00
CHEMISTRY; METALLURGY
C03C17/42
CHEMISTRY; METALLURGY
C03C17/34
CHEMISTRY; METALLURGY
B32B7/14
PERFORMING OPERATIONS; TRANSPORTING
B32B37/14
PERFORMING OPERATIONS; TRANSPORTING
B32B37/18
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The present invention relates to a fire-resistant pane, including at least one float glass pane with a tin bath side and at least one protective layer that is arranged on the tin bath side in a planar manner, wherein the float glass pane and the protective layer are thermally tempered or partially tempered together. At least one alkaline fire-resistant layer is arranged on the protective layer in a planar manner. The protective layer contains metal oxide, metal nitride, and/or mixtures or layered compounds thereof. At least one edge sealing is arranged directly on the protective layer.
Claims
1. A fire-resistant pane, comprising: a float glass pane with a tin bath side and a protective layer that is arranged on the tin bath side in a planar manner, wherein the float glass pane and the protective layer are thermally tempered or partially tempered together, at least one alkaline fire-resistant layer that is arranged on the protective layer in a planar manner, wherein the protective layer contains or comprises silicon nitride, and an edge sealing that is arranged directly on the protective layer.
2. The fire-resistant pane according to claim 1, wherein the edge sealing contains at least one of polysulfide, polyurethane, polysilicone, and reactive hotmelts.
3. The fire-resistant pane according to claim 1, wherein the fire-resistant layer contains at least one of alkali silicate, alkali phosphate, alkali tungstate, alkali molybdate, and/or mixtures or layered compounds thereof.
4. The fire-resistant pane according to claim 1, wherein the fire-resistant layer contains a hydrogel of at least one of cross-linked monomers and polymers.
5. The fire-resistant pane according to claim 1, wherein the protective layer contains tin-zinc oxide and the ratio of zinc:tin is from 5 wt.-%:95 wt.-% to 95 wt.-%:5 wt.-%.
6. The fire-resistant pane according to claim 1, wherein the protective layer contains at least one dopant.
7. The fire-resistant pane according to claim 1, wherein the protective layer is a multi-layer structure and wherein one protection sub-layer contains or is made of a metal nitride, and an other protection sub-layer contains or is made of a metal oxide.
8. The fire-resistant pane according to claim 1, wherein the protective layer has a thickness d from 2 nm to 500 nm.
9. The fire-resistant pane according to claim 1, wherein the float glass pane contains borosilicate glass, alumosilicate glass, alkaline earth silicate glass, and soda lime glass.
10. The fire-resistant pane according to claim 1, wherein the float glass pane has a thickness from 1 mm to 25 mm.
11. The fire-resistant pane according to claim 1, wherein one adhesion-improving layer or one adhesion-reducing layer is arranged between the protective layer and the fire-resistant layer.
12. The fire-resistant pane according to claim 1, wherein the fire-resistant layer contains a hydrogel of at least one of polyacrylamide, poly-N-methylolacrylamide, or polymerized 2-hydroxy-3-methacryloxy-propyl-trimethyl-ammonium chloride.
13. The fire-resistant pane according to claim 1, wherein the fire-resistant layer contains at least one of alkali polysilicate, alkali polyphosphate, alkali polytungstate, alkali polymolybdate, and mixtures or layered compounds thereof.
14. The fire-resistant pane according to claim 3, wherein the fire-resistant layer contains at least one of sodium, potassium, lithium, and mixtures thereof.
15. The fire-resistant pane according to claim 1, wherein the protective layer contains tin-zinc oxide and a ratio of zinc: tin is from 15 wt.-%:85 wt.-% to 70 wt. -%:30 wt.%.
16. The fire-resistant pane according to claim 1, wherein the protective layer contains at least one dopant and wherein the dopant is at least one of antimony, fluorine, silver, ruthenium, palladium, aluminum, and tantalum.
17. The fire-resistant pane according to claim 1, wherein the protective layer contains at least one dopant, and wherein a fraction of the dopant in a metal fraction of the protective layer is from 0 wt.-% to 10 wt.-% .
18. The fire-resistant pane according to claim 1, wherein the protective layer is a two-ply layer structure and wherein one protection sublayer contains or is made of a metal nitride and one protection sublayer contains or is made of a metal oxide.
19. The fire-resistant pane according to claim 1, wherein the protective layer is a multilayer structure and wherein one protection sublayer contains or is made of silicon nitride, and one protection sublayer contains or is made of a tin-zinc oxide or a doped tin-zinc oxide.
20. The fire-resistant pane according to claim 1, wherein the protective layer has a thickness from 5 nm to 50 nm.
21. The fire-resistant pane according to claim 1, wherein the fire-resistant layer has a thickness from 0.5 mm to 70 mm.
22. The fire-resistant pane according to claim 11, wherein the one adhesion-improving layer or one adhesion-reducing layer contains at least one organofunctional silane or at least one polymer-wax.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The invention is explained in detail in the following with reference to drawings and an example. The drawings are not completely true to scale. The invention is in no way restricted by the drawings. They depict:
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DETAILED DESCRIPTION OF THE INVENTION
(14)
(15) A protective layer 3.1 is arranged on the tin bath side II of the float glass pane 1.1 in a planar manner. The float glass pane 1.1 is thermally tempered or partially stressed together with the protective layer 3.1 such that the float glass pane 1.1 and the protective layer 3.1 bond fixedly to each other. A fire-resistant layer 3.1 made of an alkaline polysilicate is arranged on the protective layer 3.1. The protective layer 3.1 extends partially and preferably substantially completely over the entire tin bath side II of the float glass pane 1.1. The protective layer 3.1 extends, in particular, over the complete surface between the fire-resistant layer 2.1 and the float glass pane 1.1. It can thus be ensured that the surface of the tin bath side II of the float glass pane 1.1 is protected against the alkaline polysilicate of the fire-resistant layer 2.1.
(16) The protective layer 3.1 contains, for example, antimony-doped tin-zinc oxide and was deposited by cathode sputtering. The target for the deposition of the protective layer 3.1 contained 30 wt.-% zinc, 68 wt.-% tin, and 2 wt.-% antimony. The deposition took place under addition of oxygen as reaction gas during the cathode sputtering. The thickness d of the protective layer 3.1 is, for example, 25 nm.
(17) The fire-resistant layer 2.1 contains, for example, a hardened polysilicate, which is formed from an alkali silicate and at least one hardener, for example, from potassium silicate and colloidal silicic acid. In an alternative embodiment, the potassium silicate can also be produced directly from caustic potash solution and silicon dioxide. In the polysilicate, the molar ratio of silicon dioxide and potassium oxide (Si02:K20) is, for example, 4.7:1. Such a fire-resistant layer 2.1 is typically alkaline with a pH of 12. The thickness h of the fire-resistant layer 2.1 is, for example, 3 mm.
(18) An edge sealing 6 is arranged on the float glass pane 1.1 surrounding the fire-resistant layer 2.1 and along the edge of the float glass pane 1.1. The edge sealing 6 contains or is made, for example, of a sealant or adhesive based on polysulfide, polyurethane, polysilicone, or reactive hotmelts. In combination with protective layers 3.1 made of tin-zinc oxide, edge sealings 6 made of polysulfide have proved to be particularly advantageous, with good adhesion and long-term stability. The edge sealing 6 can be arranged directly on the float glass pane 1.1 with protective layer 3.1 according to the invention since, as a result of being tempered together, the protective layer 3.1 is particularly fixedly bonded to the float glass pane 1.1.
(19)
(20) Again, an edge sealing 6 is arranged between the float glass panes 1.1 and 1.2 surrounding the fire-resistant layer 2.1. The edge sealing 6 forms, together with the float glass panes 1.1 and 1.2, a hermetically sealed cavity, in which the fire-resistant layer 2.1 is protected against air and moisture from the environment. In order to keep the distance between the float glass panes 1.1 and 1.2 constant and stable during production and use, a spacer 5 can be arranged between the float glass panes 1.1 and 1.2. The spacer 5 is made, for example, of polyisobutylene or other suitable materials, and, in particular, plastics.
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(23) Such a fire-resistant glazing assembly 100 is suitable for independent use as an architectural element in a building or as a motor vehicle glazing assembly.
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(26) The triple glazing assemblies depicted in
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(29) Example 1 is a float glass pane according to the invention, whose tin bath side 1I was coated with a protective layer made of tin-zinc oxide. The ratio of tin to zinc was 50 wt.-%:50 wt.-%. The thickness d of the protective layer was 25 nm. After the aging test, clouding of 0.3% was measured.
(30) Example 2 is a float glass pane according to the invention, whose tin bath side 1I was coated with a protective layer made of zinc oxide. The thickness d of the protective layer was 25 nm. After the aging test, clouding of 0.7% was measured.
(31) Example 3 is a float glass pane according to the invention, whose tin bath side II was coated with a protective layer made of indium-tin oxide (ITO). The ratio of indium to tin was 90 wt.-%:10 wt.-%. The thickness d of the protective layer was 25 nm. After the aging test, clouding of 0.4% was measured.
(32) The Comparative Example according to the prior art was a float glass pane, of which neither the atmosphere side I nor the tin bath side II was coated and, thus, both sides were exposed to the aqueous solution of potassium silicate. After the aging test, clouding of 8.9% was measured in the case of the Comparative Example.
(33) In the aging test presented, 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 according to the invention and, thus, were directly exposed to the aqueous solution of potassium silicate. It can therefore be concluded that the clouding is caused substantially by the contact of the tin bath side II with the aqueous solution of potassium silicate.
(34) Each of the protective layers according to the invention from Examples 1 to 3 reduced the clouding of the float glass pane compared to the Comparative Example according to the prior art without a protective layer 3 according to the invention to values<1%. In the case of the protective layer according to the invention made of tin-zinc oxide according to Example 1, the clouding was actually reduced by a factor of 89. This result was unexpected and surprising for the person skilled in the art.
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(36) As investigations of the inventors revealed, already with a protective (sub)layer 3.1a made of silicon nitride that had a thickness d, of 3 nm, it was possible to obtain advantageously increased aging resistance and greatly reduced clouding. At the same time, it was possible to reduce the thickness of the tin-zinc oxide layer without degrading aging resistance or clouding.
(37) In this exemplary embodiment, the protective (sub)layer 3.1a made of silicon nitride is arranged directly on the tin bath side II of the float glass pane 1.1 and the (protective (sub)layer 3.1b made of tin-zinc oxide is arranged on the protective (sub)layer 3.1a made of silicon nitride. Of course, the order of the materials can also be permuted such that a layer made of tin-zinc oxide is arranged directly on the tin bath side of the float glass pane and a layer made of silicon nitride is arranged on the layer made of tin-zinc oxide.
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(39) Table 1 summarizes the results of aging tests and clouding tests for various exemplary embodiments of fire-resistant panes 10 according to the invention.
(40) TABLE-US-00001 TABLE 1 Layer Layer Resistance in the Material Thickness (n) Aging Test Clouding tin-zinc oxide (3.1) 25 nm (3.1) Good Slight silicon nitride (3.1a)/ 8 nm (3.1a)/ Very good Very slight tin-zinc oxide (3.1b) 15 nm (3.1b) silicon nitride (3.1a)/ 3 nm (3.1a)/ Good Slight tin-zinc oxide (3.1b) 15 nm (3.1b) tin-zinc oxide (3.1a)/ 15 nm (3.1a)/ Very good Very slight silicon nitride (3.1b) 8 nm (3.1b)
(41) The first column indicates the material of the protective layer 3.1 and the second column indicates the thickness. The protective layers 3.1 are in each case arranged directly on the float glass pane 1.1. The statement silicon nitride (3.1a)/tin-zinc oxide (3.1b) indicates that the protective layer 3.1 comprises a 2-ply layer structure. The first indicated protective (sub)layer 3.1a made of silicon nitride is arranged directly on the float glass pane 1.1 and the second protective (sub)layer 3.1b made of tin-zinc oxide is arranged directly on the first protective (sub)layer 3.1a. For the layer sequence tin-zinc oxide (3.1a)/silicon nitride (3.1b) the reverse order applies.
(42) Surprisingly, the layer sequence silicon nitride (3.1a)/tin-zinc oxide (3.1b) with layer thicknesses of 3 nm for the first protection (sub)layer 3.1a and 15 nm for the second protective (sub)layer 3.1b exhibited similarly good aging resistance and slight clouding as a single-ply protective layer 3.1 made of 25 nm tin-zinc oxide, although the overall thickness could be reduced from 25 nm to 18 nm. For layer thickness combinations of 8 nm for silicon nitride and 15 nm for tin-zinc oxide, the experiments actually revealed increased aging resistance and less clouding than with a single-ply protective layer 3.1 made of 25 nm tin-zinc oxide.
(43) As extensive investigations of the inventors revealed, 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-tin oxide, is particularly advantageous in order to produce an aging-resistant fire-resistant glazing assembly and to prevent clouding of the tin bath side of a float glass pane in the case of contact with an alkaline fire-resistant layer.
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(45) In the process step depicted in
(46) The float glass panes 1.1 and 1.2 are held at a fixed distance from one another by an external device (not shown) such that a cavity 8 is formed between the float glass panes 1.1 and 1.2, with the distance predefining the thickness of the subsequent fire-resistant layer. A further fixing can preferably take place by means of one or a plurality of spacers 5. The spacers 5 preferably run along the entire circumference of the float glass panes 1.1 and 1.2 and leave open only a filling opening 7 on, for example, the top narrow side of the cavity 8. Moreover, the narrow sides of the cavity 8 between the float glass panes 1.1 and 1.2 are sealed by an edge sealing 6. The edge sealing 6 is made of a sealant, such as polysulfide. The edge sealing 6 is arranged on the full circumference of the cavity 8 with the exception of the region of the filling opening 7.
(47) In the process step depicted in
(48) Table 2 summarizes the results of the aging tests on various exemplary embodiments of fire-resistant glazing assemblies 100 according to the invention. The examples presented correspond with the exception of the differences identified to the exemplary embodiment of
(49) TABLE-US-00002 Resistance and seal Fire-resistant glazing tightness of the edge assembly with: sealing in the aging test Clouding Example A Float glass pane 1.1 and Poor Slight protective layer 3.1 made of tin-zinc oxide on the tin bath side II, not tempered together Example B Float glass pane 1.1 and Very good Slight protective layer 3.1 made of tin-zinc oxide on the tin bath side II, tempered together
(50) The fire-resistant glazing assembly according to the invention of Example B contained a float glass pane 1.1 and a protective layer 3.1 made of tin-zinc oxide on the tin bath side II of the float glass pane 1.1. The float glass pane 1.1 and the protective layer 3.1 were thermally tempered together. This means that, first, the protective layer 3.1 was deposited on the tin bath side II of the float glass pane 1.1 and, then, the coated float glass pane 1.1 was thermally tempered.
(51) In contrast, in the case of the fire-resistant pane according to Example A, the float glass pane 1.1 was first thermally tempered, and, then, a protective layer 3.1 made of tin-zinc oxide was applied on the tin bath side II of the float glass pane 1.1.
(52) Both fire-resistant glazing assemblies exhibited only slight clouding during aging. The protective layers 3.1 made of tin-zinc oxide were able in each case to protect the tin bath sides II of the float glass panes 1.1 against the attack of the alkaline fire-resistant layers 2.1.
(53) However, in the aging test, significant differences appeared in the region of the edge sealing: In Example A, defects in the adhesion and seal tightness of the edge sealing could be noted. Thus, it was possible for air to penetrate into the interior of the fire-resistant glazing assembly; it was possible for water to escape from the fire-resistant compound and damage the fire-resistant glazing assemblies. Such fire-resistant glazing assemblies are not very useful. Consequently, such a protective layer in the region of the edge sealing must be removed with considerable effort, for example, by mechanical grinding or chemical etching, before the application of the edge sealing.
(54) In the case of Example B, the adhesion and seal tightness of the edge sealing was significantly improved. The adhesion of the edge sealing on the protective layer 3.1 of the float glass pane 1.1 tempered together was stable and did not lose its bonding to the float glass pane 1.1, even after many aging cycles. This can be explained by the fact that the float glass pane 1.1 and the protective layer 3.1 form a stable bond by being thermally tempered or partially tempered together that prevents detachment or dissolution of the protective layer 3.1 between the edge sealing 6 and the float glass pane 1.1. Complicated removal of the protective layer 3.1 in the area of the edge sealing is no longer necessary.
(55) This result was unexpected and surprising for the person skilled in the art.