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JP-7857227-B2 - Coating substrate

JP7857227B2JP 7857227 B2JP7857227 B2JP 7857227B2JP-7857227-B2

Inventors

  • フーベルト， ジュリー
  • メルシエ， ヴィルジニー
  • 臼井 玲大

Assignees

  • エージーシー グラス ユーロップ
  • ＡＧＣ株式会社

Dates

Publication Date
20260512
Application Date
20210401
Priority Date
20200402

Claims (20)

  1. A coated substrate comprising a transparent substrate having two main, opposite first and second surfaces, wherein a functional coating is provided on at least one surface, the transparent substrate being provided with a topcoat on and in contact with the functional coating, which is magnetron sputtered with a mixed metal oxide containing at least SiO x , TiO y , and ZrO z (where x, y, and z are in the range of 1.8 to 2.2), The top coat contains only silicon, titanium, zirconium, and optionally impurities as metal atoms. The impurities are yttrium, hafnium, and/or aluminum. The top coat, excluding impurities, is a total of 100 atomic percent of metal. - 15 to 60 atomic percent silicon, -8 to 35 atomic percent titanium, - 30 to 70 atomic percent zirconium, Includes, A coated substrate characterized by having a top coat thickness of 0.1 to 10 nm.
  2. The coated substrate according to claim 1 , wherein the functional coating is a solar control coating, a conductive coating, an anti-reflective coating, a decorative coating, and/or a low-emissivity coating.
  3. The coated substrate according to claim 1 or 2 , wherein the functional coating is a single-layer metal oxide coating, a multi-layer metal oxide coating, a non-metal oxide coating, or a multi-layer coating.
  4. The coated substrate according to claim 3, wherein the single-layer metal oxide coating comprises zinc oxide doped with aluminum, gallium, or hafnium; a mixed metal oxide of zinc and tin; tin oxide; tin oxide doped with fluorine or antimony; indium oxide; or indium oxide doped with tin .
  5. The coated substrate according to claim 3 , wherein the multilayer metal oxide coating comprises at least one layer of a high refractive index material and at least one layer of a low refractive index material.
  6. The coated substrate according to claim 3, wherein the multilayer coating includes an alternating arrangement of n infrared reflective (IR) layers and n+ 1 dielectric layers, such that each IR layer is surrounded by two dielectric layers, and n ≥ 1.
  7. Multilayer coating, a. At least one silver layer, in the order of substrate/MeO/ZnO:AlSi/Ag/AlSi-MeO, where MeO is a metal oxide; or b. A first dielectric layer containing silicon nitride; a first layer containing Ni or NiCr; an infrared (IR) reflective layer containing silver; a second layer containing Ni or NiCr; a second dielectric layer containing silicon nitride; or c. An infrared (IR) reflective layer in contact with and sandwiched between the first and second layers, wherein the second layer comprises NiCrOx; at least the NiCrOx-containing second layer is oxidized in steps such that a first portion of the second layer closer to the infrared (IR) reflective layer is oxidized less than a second portion of the second layer further away from the infrared (IR) reflective layer; or d. A dielectric layer; a first layer containing zinc oxide located on the dielectric layer; an infrared (IR) reflective layer containing silver located on and in contact with the first layer containing zinc oxide; a layer containing NiCr oxide located on and in contact with the IR reflective layer; a second layer containing zinc oxide located on and in contact with the layer containing NiCr oxide; another dielectric layer located on the second layer containing zinc oxide; or e. A first dielectric layer; a first infrared (IR) reflective layer containing silver located at least on the first dielectric layer; a first layer containing zinc oxide located at least on the first IR reflective layer and the first dielectric layer; a second IR reflective layer containing silver located on and in contact with the first layer containing zinc oxide; a layer containing NiCr oxide located on and in contact with the second IR reflective layer; a second layer containing zinc oxide located on and in contact with the layer containing NiCr oxide; at least another dielectric layer located on the second layer containing zinc oxide; or f. A first dielectric layer; a first layer containing zinc oxide located on the dielectric layer; an infrared (IR) reflective layer containing silver located on and in contact with the first layer containing zinc oxide; a second layer containing zinc oxide located on the IR layer; a second dielectric layer located on the second layer containing zinc oxide; or g. A first dielectric layer; a first IR layer containing silver; a second dielectric layer; a second IR layer; a third dielectric layer, where the first, second, and third dielectric layers may include multiple layers; or h. A first dielectric layer; a first IR layer containing silver; a second dielectric layer; a second IR layer; a third dielectric layer; a third IR layer; a fourth dielectric layer, where the first, second, third, and fourth dielectric layers may include multiple layers. A coating substrate according to claim 6 , including the following:
  8. The coated substrate according to claim 7 , wherein the metal oxide MeO in at least one silver layer of the multilayer coating is SnO₂ , TiO₂ , In₂O₃ , Bi₂O₃ , ZrO₂ , Ta₂O₅ , SiO₂ , or Al₂O₃ , or a mixture thereof .
  9. A coated substrate according to any one of claims 1 to 8, having a first functional coating on at least a portion of a first surface and a second functional coating on at least a portion of a second surface, wherein at least one of the first or second functional coatings is provided with a top coat according to any one of claims 1 to 8 .
  10. A coating substrate according to any one of claims 1 to 8 , wherein at least one temporary protective layer is further provided on and in contact with a topcoat on which a mixed metal oxide has been magnetron sputtered.
  11. The coated substrate according to claim 10 , wherein the temporary protective layer is a carbon temporary protective layer, a polymer temporary protective layer, or a peelable protective layer.
  12. A heat-treated coated substrate comprising a transparent substrate having two opposite surfaces, wherein a functional coating is provided on at least one surface, the transparent substrate being provided with a topcoat on and in contact with the functional coating, which is magnetron sputtered with a mixed metal oxide comprising at least SiO x , TiO y , and ZrO z (where x, y, and z are in the range of 1.8 to 2.2), The top coat contains only silicon, titanium, zirconium, and optionally impurities as metal atoms. The impurities are yttrium, hafnium, and/or aluminum. The top coat, excluding impurities, is 100 atomic percent of metal in total. - 15 to 60 atomic percent silicon, -8 to 35 atomic percent titanium, - 30 to 70 atomic percent zirconium, Includes, A coated substrate characterized by having a top coat with a thickness of 0.1 to 10 nm.
  13. A multilayer glazing unit comprising at least one coating substrate according to any one of claims 1 to 11 .
  14. A method for manufacturing a coated substrate, in order: (1) A step of providing a transparent substrate having two main, opposite first and second surfaces, (2) A step of depositing a functional coating on at least a portion of the first surface of a transparent substrate, (3) A step of depositing a topcoat on and in contact with the functional coating by magnetron sputtering technology, the topcoat comprising a mixed metal oxide including at least SiO x , TiO y , and ZrO z (where x, y, and z are in the range of 1.8 to 2.2), The top coat contains only silicon, titanium, zirconium, and optionally impurities as metal atoms. The impurities are yttrium, hafnium, and/or aluminum. The top coat, excluding impurities, is 100 atomic percent of metal in total. - 15 to 60 atomic percent silicon, -8 to 35 atomic percent titanium, - 30 to 70 atomic percent zirconium, Includes, The top coat has a thickness of 0.1 to 10 nm. A manufacturing method comprising at least the following.
  15. A method for manufacturing a heat-treated coated substrate, in order: (1) A step of providing a transparent substrate having two main, opposite first and second surfaces, (2) A step of depositing a functional coating on at least a portion of the first surface of a transparent substrate, (3) A step of depositing a topcoat on and in contact with the functional coating by magnetron sputtering technology, the topcoat comprising a mixed metal oxide including at least SiO x , TiO y , and ZrO z (where x, y, and z are in the range of 1.8 to 2.2), The top coat contains only silicon, titanium, zirconium, and optionally impurities as metal atoms. The impurities are yttrium, hafnium, and/or aluminum. The top coat, excluding impurities, is 100 atomic percent of metal in total. - 15 to 60 atomic percent silicon, -8 to 35 atomic percent titanium, - 30 to 70 atomic percent zirconium, Includes, The top coat has a thickness of 0.1 to 10 nm. (4) A step of heat treatment of the coating substrate, A manufacturing method comprising at least the following.
  16. A method for manufacturing a double-sided coated substrate, in order: (1) A step of providing a transparent substrate having two main, opposite surfaces, a first and a second surface, wherein the first surface is exposed. (2) A step of depositing a first functional coating on at least a portion of the first surface of a transparent substrate, (3) A step of depositing a topcoat on and in contact with the first functional coating by magnetron sputtering technique, the topcoat comprising a mixed metal oxide including at least SiO x , TiO y , and ZrO z (where x, y, and z are in the range of 1.8 to 2.2), The top coat contains only silicon, titanium, zirconium, and optionally impurities as metal atoms. The impurities are yttrium, hafnium, and/or aluminum. The top coat, excluding impurities, is a total of 100 atomic percent of metal. - 15 to 60 atomic percent silicon, -8 to 35 atomic percent titanium, - 30 to 70 atomic percent zirconium, Includes, A step in which the top coat has a thickness of 0.1 to 10 nm, (4) The step of turning the substrate over so that the second surface is exposed, (5) A step of depositing a second functional coating on at least a portion of the second surface of a transparent substrate to form a double-sided coated transparent substrate. A manufacturing method comprising at least the following.
  17. A method for producing a double-sided coated substrate according to claim 16 , the step of (6) after step (5) depositing a topcoat comprising a mixed metal oxide comprising at least SiO x , TiO y , and ZrO z (where x, y, and z are in the range of 1.8 to 2.2) on and in contact with the second functional coating by magnetron sputtering technique, The top coat contains only silicon, titanium, zirconium, and optionally impurities as metal atoms. The impurities are yttrium, hafnium, and/or aluminum. The top coat, excluding impurities, is 100 atomic percent of metal in total. - 15 to 60 atomic percent silicon, -8 to 35 atomic percent titanium, - 30 to 70 atomic percent zirconium, Includes, The top coat has a thickness of 0.1 to 10 nm. A manufacturing method that includes this.
  18. A method for manufacturing a double-sided coated substrate according to claim 17 , comprising the step of (7) heat-treating the double-sided coated transparent substrate after step (6), A manufacturing method that includes this.
  19. The method according to any one of claims 14 to 18, wherein the deposition of a topcoat containing at least silicon, titanium, and zirconium by magnetron sputtering is carried out using a target that is either metal or ceramic in order to obtain at least three elements of titanium , zirconium, or silicon .
  20. The method according to any one of claims 14 to 18 , wherein the deposition of a topcoat containing at least silicon, titanium, and zirconium by magnetron sputtering is carried out using a ceramic target containing titanium and zirconium oxides and metallic silicon.

Description

The present invention relates to a coated substrate provided with a functional coating and a magnetron sputtered topcoat of a mixed metal oxide containing at least SiO x , TiO y , and ZrO z , a method for providing the coated substrate, and the use of the topcoat. Functional coatings, such as those containing magnetron-sputtered dielectric layers, are typically known to be susceptible to chemical and mechanical damage during their manufacture, transport, processing, storage, and/or handling. This limited mechanical resistance, chemical resistance, and corrosion resistance usually restricts their feasible use in contact with the external environment. Various attempts are being made to provide glazing with coatings that have high chemical or mechanical durability, or both. International Publication No. 2009115596A1 relates to a glazing comprising a thin-layer assembly deposited in a vacuum using a magnetron, which is essentially transparent and has lightfast and/or low emission properties, wherein the surface protective layer comprises a layer comprising titanium oxide and at least one other high-hardness metal oxide selected from the group including ZrO₂ , SiO₂ , and Cr₂O₃ . The glazing disclosed above can withstand heat treatment at 550°C for 5 minutes without causing optical defects such as discoloration or pearlescent luster. In the mixed oxide, titanium oxide is present in a ratio of at least 40% by weight. The surface layer contains zirconium oxide in a ratio of 15 to 50% by weight. International Publication No. 2010031808A1 relates to a glazing comprising at least one layer deposited by cathode spraying under vacuum, wherein the layer contains one or more oxides, and the weight ratio of titanium oxide is at least 40% and 95% or less. The thickness of the layer in question, and optionally the thickness of another layer containing a metal oxide, is selected such that the layer provides at least 15% reflectance and at least 60% light transmittance on a 4 mm thick transparent "float" glass sheet. The layer or layer system in question further possesses mechanical resistance and/or chemical resistance equivalent to that of a layer produced by thermal decomposition to obtain a product having the same type of optical properties. However, the above solutions do not provide sufficient mechanical durability against the wear encountered during transport and storage conditions in typical dry brush tests and/or Automatic Wet Rub Tests (AWRTs). International Publication No. 2018202595A1 relates to a coated substrate comprising a substrate, a soft coating provided on at least a portion of at least one surface of the substrate, a protective sol-gel coating provided on at least a portion of the said surface on the soft coating, a method for manufacturing such a coated substrate, and a glazing unit comprising such a coated substrate. The sol-gel coating comprises a mixture of titanium dioxide, silicon dioxide, and optionally bismuth oxide and/or cerium oxide in a theoretical weight ratio of titanium dioxide ( TiO₂) to silicon dioxide ( SiO₂) in the range of 0.10 to 3. If zirconium oxide is present, the zirconium oxide/silicon oxide ratio is in the range of 0.10 to 3. The titanium dioxide/zirconium oxide ratio is in the range of 0.10 to 10. The thickness of the sol-gel coating is typically in the range of 50 to 500 nm. The main drawback of this solution is the formation of a very thick protective layer, the need for an additional essential heating step to cure the sol-gel coating, and the resulting need for modifications to the production line, thus imposing further manufacturing constraints. In other words, an intermediate step is required where damage may occur before the coated substrate is protected by the sol-gel coating. This topcoat is a magnetron-sputtered mixed metal oxide containing at least SiO x , TiO y , and ZrO z (where x, y, and z are in the range of 1.8 to 2.2), The top coat is made up of 100 atomic percent of metal, including impurities. -10 to 65 atomic percent silicon (Si), -8 to 38 atomic percent titanium (Ti), -25 to 80 atomic percent zirconium (Zr), Includes, The top coat has a thickness of 0.1 to 10 nm. Impurities are considered additional metals that are substantially inseparable from the above metals. This is especially true for yttrium and/or hafnium. Where these additional metals are present, their content remains relatively limited, not exceeding 1 atomic percent of the total, and typically remaining at less than 0.8 atomic percent. These are not considered in the calculation of the effective content of the topcoat. The above effective content is considered as the sum of only the contributions of titanium, zirconium, and silicon, which provide mechanical durability within the scope of the invention. Aluminum may be present as a trace element in amounts of <2.0 atomic percent or <1.0 atomic percent. In some embodiments of the present invention, the above ranges of Si, Ti, and Zr in the topcoat c