Silver-free solar control coated glass

Abstract

The invention relates to a multi-layer coated (20) glass (10) configured for use in architectural applications and vehicles.

Description

[0001] SILVER-FREE SOLAR CONTROL COATED GLASS

[0002] TECHNICAL FIELD

[0003] The invention relates to a multi-layer coating that is daylight permeable, used in thermal insulation glasses and does not contain silver.

[0004] BACKGROUND

[0005] One of the factors that differentiate the optical properties of the glass is the coating applications made on its surface. One of the coating applications is the magnetic field- supported sputtering method in a vacuum environment. It is a frequently used method in the production of architectural and automotive coatings with low-e properties. The permeability and reflection values of the glass coated with said method in the visible, near-infrared, and infrared regions can be obtained at the targeted levels.

[0006] Apart from the permeability and reflection values, the selectivity value in coated glasses is also an important parameter. Selectivity is defined as the ratio of the visible region permeability value to the solar factor in the ISO 9050 (2003) standard. The number of functional layers in which the selectivity values of the coatings are included, the type of nucleating layer used can be kept at the targeted levels with the parametric optimizations of the layers.

[0007] The invention with publication number EP3033312 Bl relates to a low-e coated glass product. The coating comprises a first infrared reflective layer and a second infrared reflective layer separated from each other by contact layers and dielectric layers. Coated glass has low visible permeability. The infrared reactive layers in the coating are surrounded by contact layers containing NiCr. Also, the coating comprises NiCr layer on the second infrared reflective layer and in contact, SiN layer on the NiCr layer and in contact, and ZrO on the SiN layer and in contact. BRIEF DESCRIPTION OF THE INVENTION

[0008] The present invention relates to a multi-layer coating in order to bring new advantages to the related technical field.

[0009] The main object of the invention is to provide a multi-layer coating with a low emissivity value.

[0010] Another object of the invention is to provide a multi-layer coating suitable for single glass use.

[0011] Another object of the invention is to provide a heat treatable multi-layer coating.

[0012] Another object of the invention is to provide a multi-layer coating with high mechanical strength.

[0013] In order to accomplish all of the above-mentioned objects and those which will emerge from the detailed description below, the present invention is a multilayer coated glass configured for use in architectural applications and vehicles. Accordingly, said invention is characterized in that the emissivity value of said multi-layer coating is between 0.2 and 0.5 and that

[0014] - it comprises a first functional layer positioned between a lower dielectric layer and a middle dielectric layer; a second functional layer positioned between said middle dielectric layer and an upper dielectric structure; and

[0015] - that the ratio of the first functional layer thickness to the second functional layer thickness is less than 0.6,

[0016] - the optical path of the middle dielectric layer is between 65 nm and 235 nm,

[0017] - the upper dielectric structure comprises a final layer (262) preferably containing TiOx with a thickness of 1 nm to 10 nm.

[0018] A preferred embodiment of the invention is that the upper dielectric structure comprises an upper dielectric layer comprising at least one of SiOxNy or SiNx positioned below the final layer comprising TiOx. A preferred embodiment of the invention is to use the multi-layer coating in contact with the atmosphere.

[0019] Another preferred embodiment of the invention is that the first functional layer and the second functional layer comprise TiOxNy.

[0020] A preferred embodiment of the invention is that the middle dielectric layer comprises at least one or more of ZnAlOx, ZnSnOx, SnOx, TaOx, TaOxNy, TiOx, TiOxNy, TiZrOx, ZrOx, ZrOxNy, SiZrOx, SiZrOxNy, WZrOx, WZrOxNy, NbOx, NbZrOx, MoOx, MoOxNy’ NbZrOx. The middle dielectric layer (23) may also include SiNx or SiOxNy or SiOx in addition to the materials given above.

[0021] Another preferred embodiment of the invention is that the middle dielectric layer comprises NbOx.

[0022] Another preferred embodiment of the invention is that the multi-layer coating optionally comprises a metallic layer.

[0023] Another preferred embodiment of the invention is that said metallic layer contacts at least one of the first functional layer and the second functional layer.

[0024] Another preferred embodiment of the invention is that said metallic layer is at most 10 nm.

[0025] BRIEF DESCRIPTION OF THE FIGURE

[0026] Figure 1 shows a representative view of the multi-layer coating.

[0027] Figure 2 shows a representative alternative view of the multi-layer coating.

[0028] Figure 3 shows a representative alternative view of the multi-layer coating.

[0029] Figure 4 shows a representative alternative view of the multi-layer coating.

[0030] Figure 5 shows a representative view of the multi-layer coating without a metallic layer. REFERENCE NUMBERS GIVEN IN THE FIGURE

[0031] 10 Glass

[0032] 20 Multi-layer Coating

[0033] 21 Lower Dielectric Layer

[0034] 22 First Functional Layer

[0035] 23 Middle Dielectric Layer

[0036] 24 Metallic Layer

[0037] 25 Second Functional Layer

[0038] 26 Upper Dielectric Structure

[0039] 261 Upper Dielectric Layer

[0040] 262 Final layer

[0041] DETAILED DESCRIPTION OF THE INVENTION

[0042] The multi-layer coating (20) of the invention is explained with examples that do not have any limiting effect only for a better understanding of the subject in this detailed description.

[0043] The production of multi-layer coated (20) glasses (10) for architectural and automotive purposes is carried out by sputter coating method (also known as sputtering in the art). The present invention relates generally to multi-layer coated (20) glasses (10) used as daylight permeable and heat insulating glass (10), the content and application of said multi-layer coating (20). The multi-layer coated (20) glass (10), which is the subject of the invention, can also be used in heat glass units and laminated structures for the architectural and automotive sectors.

[0044] The term "optical performance" mentioned in the invention refers to the visible region light transmittance (hereinafter referred to as %Tvis), total solar energy transmittance, visible region internal and external reflection values and CIE L*, a*, b* color values in single glass use for multi-layer coated (20) glass (10) in single glass second face use.

[0045] The refractive indices of all layers in the multi-layer coated (20) glass (10), which is the subject of the invention, were determined using computational methods over optical constants obtained from single layer measurements. These refractive indices are refractive index data at 550 nm.

[0046] The following data were determined as a result of experimental studies carried out to improve the multi-layer coating (20) sequence preferred both in terms of ease of production and optical properties.

[0047] A multi-layer coating (20) consisting of a plurality of metal, metal oxide and metal nitride / oxy nitride layers located on the surface of the glass (10) was developed using the sputter method to obtain a multi-layer coated (20) glass (10) designed to be heat treatable (suitable for use as both heat-treated and without heat treatment). The layers are deposited on each other in a vacuum one after the other. At least one and / or several of tempering, partial tempering, annealing, lamination and bending processes can be used together as heat treatment.

[0048] In the multi-layer coating (20), which is the subject of the invention, a lower dielectric layer (21) containing at least one layer in the dielectric structure in contact with the glass (10) is used. The lower dielectric layer (21) comprises at least one or more of the materials SixNy, SiOx, SiOxNy, ZnAINx, ZnAlOx, ZnAlOxNy, ZnSnNx, ZnSnOx, ZnSnOxNy, TaOx, TaOxNy, TiOx, TiNx, TiOxNy, TiSiZrOxNy, ZrNx, ZrOx, ZrOxNy, SiZrN, SiZrOx, SiZrOxNy, WZrOx, NbNx, NbOx, NbOxNy, NbZrOx. In the preferred embodiment, the lower dielectric layer (21) comprises SiOxNy. In another alternative embodiment, the lower dielectric layer (21) comprises SiNx.

[0049] In another embodiment of the invention, the lower dielectric layer (21) comprises SiNx together with SiOxNy. Thus, it prevents ion migration more effectively than single layer use.

[0050] In another embodiment of the invention, the lower dielectric layer (21) comprises TiOx together with SiNx and / or SiOxNy. Thus, the visible region reflection values of the multilayer coated (20) glass (10) can be reduced.

[0051] In another embodiment of the invention, the lower dielectric layer (21) comprises NbZrOx together with SiNx and / or SiOxNy. The lower dielectric layer (21) serves the purpose of preventing alkali ion migration, which is facilitated at high temperature, by acting as a diffusion barrier. Thus, the lower dielectric layer (21) supports the resistance of the multi-layer coating (20) to heat treatment processes. The refractive index value of the materials used in the lower dielectric layer (21) is between 1.45 and 2.7.

[0052] The thickness of the lower dielectric layer (21) is between 40 nm and 85 nm. In the preferred embodiment, the thickness of the lower dielectric layer (21) is between 45 nm and 80 nm. Most preferably, the thickness of the lower dielectric layer (21) is between 50 nm and 75 nm. Thanks to the use of a thick lower dielectric layer (21), the visible region internal reflection values of the multi-layer coating (20) are <20% and the external reflection values are <25%.

[0053] The first functional layer (22) is positioned on the lower dielectric layer (21). The first functional layer (22) contacts the lower dielectric layer (21). The first functional layer (22) comprises at least one or more of the materials NbZrNx, NbZrOxNy, TiNx, TiOxNy, NbNx, NbOxNy, TiZrNx, TiZrOxNy together.

[0054] In the preferred embodiment, the first functional layer (22) comprises TiOxNy. In one embodiment of the invention, the first functional layer (22) comprises NbZrNx. In another embodiment of the invention, the first functional layer (22) comprises NbZrOxNy. In another embodiment of the invention, the first functional layer (22) comprises TiNx. In another embodiment of the invention, the first functional layer (22) comprises NbNx. In another embodiment of the invention, the first functional layer (22) comprises NbOxNx. In another embodiment of the invention, the first functional layer (22) comprises TiZrNx. In another embodiment of the invention, the first functional layer (22) comprises TiZrOxNy.

[0055] The thickness of the first functional layer (22) is between 4 nm and 22 nm. In the preferred embodiment, the thickness of the first functional layer (22) is between 6 nm and 18 nm. Most preferably, the thickness of the first functional layer (22) is between 8 nm and 15 nm. In this way, the first functional layer (22) adds solar control to the structure.

[0056] On the first functional layer (22), the middle dielectric layer (23) containing at least one layer in the dielectric structure is positioned. The refractive index value of the materials used in said middle dielectric layer (23) varies between 1.45 and 2.7. The middle dielectric layer (23) comprises at least one or more of the materials ZnAlOx, ZnSnOx, SnOx, TaOx, TaOxNy, TiOx, TiOxNy, TiZrOx, ZrOx, ZrOxNy, SiZrOx, SiZrOxNy, WZrOx, WZrOxNy, NbOx, NbOxNy, NbZrOx, NbZrOxNy, MoOx, MoOxNy. The middle dielectric layer (23) may also include SiNx or SiOxNy or SiOx in addition to the materials given above.

[0057] Optionally, a metallic layer (24) may be positioned adjacent to the middle dielectric layer (23). In order to maintain the properties of the metallic layer (24) or the first functional layer (22) adjacent to the middle dielectric layer (23), it is necessary to use minimum reactive gas in the process. Therefore, materials that require less oxygen during the process are preferred as the middle dielectric layer (23).

[0058] The use of a layer comprising Nb and / or Zr as the middle dielectric layer (23) improves the mechanical and chemical strength of the multi-layer coated (20) glass (10).

[0059] In the preferred embodiment, the middle dielectric layer (23) comprises NbOx.In another embodiment of the invention, the middle dielectric layer (23) comprises NbNy. In another embodiment of the invention, the middle dielectric layer (23) comprises NbOxNy. In another embodiment of the invention, the middle dielectric layer (23) comprises NbZrOx. In another embodiment of the invention, the middle dielectric layer (23) comprises NbZrOxNy. In another embodiment of the invention, the middle dielectric layer (23) comprises NbZrNy.

[0060] In another embodiment of the invention, the middle dielectric layer (23) comprises ZrOx. In another embodiment of the invention, the middle dielectric layer (23) comprises ZrOxNy. In another embodiment of the invention, the middle dielectric layer (23) comprises ZrNx.

[0061] In one embodiment of the invention, the middle dielectric layer (23) comprises ZnAlOx. In another embodiment of the invention, the middle dielectric layer (23) comprises ZnSnOx. In another embodiment of the invention, the middle dielectric layer (23) comprises SnOx. In another embodiment of the invention, the middle dielectric layer (23) comprises TaOx. In another embodiment of the invention, the middle dielectric layer (23) comprises TaOxNy. In another embodiment of the invention, the middle dielectric layer (23) comprises TiOx. In another embodiment of the invention, the middle dielectric layer (23) comprises TiOxNy. In another embodiment of the invention, the middle dielectric layer (23) comprises TiZrOx. In another embodiment of the invention, the middle dielectric layer (23) comprises SiOxNy. In another embodiment of the invention, the middle dielectric layer (23) comprises SiNx. In another embodiment of the invention, the middle dielectric layer (23) comprises SiZr Ox. In another embodiment of the invention, the middle dielectric layer (23) comprises SiZr OxNy. In another embodiment of the invention, the middle dielectric layer (23) comprises WZrOx. In another embodiment of the invention, the middle dielectric layer (23) comprises WZrOxNy. In another embodiment of the invention, the middle dielectric layer (23) comprises MoOx. In another embodiment of the invention, the middle dielectric layer (23) comprises MoOxNy.

[0062] The optical path of the middle dielectric layer (23) is between 65 nm and 235 nm. In the preferred embodiment, the optical path of the middle dielectric layer (23) is between 75 nm and 210 nm. Most preferably, the optical path of the middle dielectric layer (23) is between 85 nm and 200 nm. Thus, the desired color performance and optical permeability performance can be obtained. In addition, it contributes to the heat treatment resistance.

[0063] The second functional layer (25) is positioned on the middle dielectric layer (23). The second functional layer (25) comprises at least one or more of the materials NbZrNx, NbZrOxNy, TiNx, TiOxNy, NbNx, NbOxNy, TiZrNx, TiZrOxNy together. In the preferred embodiment, the second functional layer (25) comprises TiOxNy.

[0064] In the preferred embodiment, the second functional layer (25) comprises TiOxNy. In one embodiment of the invention, the second functional layer (25) comprises NbZrNx. In another embodiment of the invention, the second functional layer (25) comprises NbZrOxNy. In another embodiment of the invention, the second functional layer (25) comprises TiNx. In another embodiment of the invention, the second functional layer (25) comprises NbNx. In another embodiment of the invention, the second functional layer (25) comprises NbOxNx. In another embodiment of the invention, the second functional layer (25) comprises TiZrNx. In another embodiment of the invention, the second functional layer (25) comprises TiZrOxNy.

[0065] The thickness of the second functional layer (25) is between 10 nm and 50 nm. In the preferred embodiment, the thickness of the second functional layer (25) is between 15 nm and 45 nm. Most preferably, the thickness of the second functional layer (25) is between 20 nm and 40 nm. Thus, solar control is added to the structure. There is an upper dielectric structure (26) containing at least one dielectric layer at the top of the low-e coating (20). The upper dielectric structure (26) comprises at least one layer in the preferred embodiment. The refractive index values of the materials used in the layers forming the upper dielectric structure (26) are between 1.45 and 2.7. The upper dielectric structure (26) comprises an upper dielectric layer (261). In an alternative embodiment, the upper dielectric structure (26) comprises the upper dielectric layer (261) and an final layer (262) positioned on it.

[0066] The upper dielectric layer (261) comprises at least one or more of the following materials: ZnAlOx, ZnSnOx, SnOx, TaOx, TaOxNy, TiOx, TiOxNy, TiZrOx, ZrOx, ZrOxNy, SiNx, SiOxNy, SiZrOx, SiZrOxNy, WZrOx, WZrOxNy, NbOx, NbZrOx, MoOx, MoOxNy. In the preferred embodiment, the upper dielectric layer (261) comprises SiOxNy. In an alternative embodiment, the upper dielectric layer (261) comprises SiNx. The optical path of the upper dielectric layer (261) varies between 55 nm and 170 nm. In the preferred embodiment, the optical path of the upper dielectric layer (261) varies between 65 nm and 160 nm. Most preferably, the optical path of the upper dielectric layer (261) varies between 75 nm and 150 nm. With the use of an upper dielectric layer (261) containing a thick SiOxNy, it is ensured that the metallic layer (24) and / or the second functional layer (25) is less affected by the heat treatment processes.

[0067] The final layer (262) comprises at least one or more of the materials ZnAlOx, ZnSnOx, SnOx, TaOx, TaOxNy, TiOx, TiOxNy, NbOx, MoOx, MoOxNy. In the preferred embodiment, the final layer (262) comprises TiOx.

[0068] The physical thickness of the final layer (262) varies between 1 nm and 6 nm. In the preferred embodiment, the physical thickness of the final layer (262) varies between 1 nm and 5 nm. Most preferably, the physical thickness of the final layer (261) varies between 1 nm and 4 nm. It is important to use the final layer (261) as a thin layer in order to achieve the desired color performance. In addition, the final layer (261) has the role of protecting the multi-layer coating (20) from external factors.

[0069] The multi-layer coating (20) comprises a metallic layer (24) that is optionally used in its structure. In case of use, said metallic layer (24) contacts at least one of the first functional layer (22) or the second functional layer (25). The metallic layer (24) may consist of at least one or more of Nb, Zr, Ti, Ta, Ni, Cr, Al, Mo, W and / or alioys thereof. The metallic layer (24) is not in oxide form. Preferably, Ti is used as the metallic layer (24).

[0070] The coating of the metallic layer (24) takes place in the argon atmosphere without reactive gas during the coating process. However, if the neighboring layers that the metallic layer is in contact with are coated in the reactive gas atmosphere, it may be that the metallic layer contains elements such as oxygen, nitrogen, etc. during and / or after the coating and / or with a second thermal process.

[0071] In one embodiment of the invention, Nb is used as the metallic layer (24). In one embodiment of the invention, Zr is used as the metallic layer (24). In one embodiment of the invention, Ta is used as the metallic layer (24). In one embodiment of the invention, Ni is used as the metallic layer (24). In one embodiment of the invention, Cr is used as the metallic layer (24). In one embodiment of the invention, Al is used as the metallic layer (24). In one embodiment of the invention, Mo is used as the metallic layer (24). In one embodiment of the invention, W is used as the metallic layer (24).

[0072] The thickness of the metallic layer (24) is at most 10 nm. In the preferred embodiment, the metallic layer thickness (24) is at most 9 nm. Most preferably, the thickness of the metallic (24) layer is between 0.1 nm and 8 nm. With the use of a metallic layer of this thickness, the heat gain coefficient of the structure (known as the total solar heat gain coefficient in the art) can be kept at low levels.

[0073] The visible region permeability of the multi-layer coating (20) in single glass use is between 20% and 50%. Meanwhile, the emissivity value of the multi-layer coating (20) is between 0.20 and 0.50.

[0074] In addition, there is a relationship between the thickness of the second functional layer (25) and the thickness of the first functional layer (22) in the multi-layer coating (20) as follows.

[0075] Thickness of the first functional layer (22) / Thickness of the second functional layer (25) <0.6

[0076] Thanks to the ratio between the above-mentioned functional layers, the permeability value of the multi-layer coating (20) and the emissivity value can be kept within the specified ranges. The multi-layer coated (20) glass (10), which is the subject of the invention, is also suitable for use as a single glass (10) except for the use of IGU. If it is used as a single glass (10), its mechanical and chemical resistance must be high since the coating will come into contact with the outside environment. In tests conducted according to EN 1096-2 standard, multilayer coated (20) glass (10) meets the requirements of class A.

[0077] The protection scope of the invention is specified in the attached claims and cannot be limited to those explained in this detailed description for illustrative purposes. It is evident that a person skilled in the art may exhibit similar embodiments in light of above-mentioned facts without departing from the main theme of the invention.

Claims

CLAIMS1. The invention relates to a multi-layer coated (20) glass (10) configured for use in architectural applications and vehicles, characterized in that said multi-layer coating (20) has an emissivity value between 0.2 and 0.5 and that it comprises- a first functional layer (22) positioned between a lower dielectric layer (21) and a middle dielectric layer (23);- a second functional layer (25) positioned between said middle dielectric layer (23) and an upper dielectric structure (26); and- that the ratio of the first functional layer (22) thickness to the second functional layer (25) thickness is less than 0.6,- the optical path of the middle dielectric layer (23) is between 65 nm and 235 nm,- the upper dielectric structure comprises a final layer (262) preferably containing TiOx with a thickness of 1 nm to 10 nm.

2. A multi-layer coated (20) glass (10) according to claim 1, characterized in that the upper dielectric structure comprises an upper dielectric layer (261) comprising at least one of SiOxNy or SiNx positioned below the TiOx-containing final layer (262).

3. A multi-layer coated (20) glass (10) according to claim 1, characterized in that the multi-layer coating (20) on the surface of the glass (10) comes into contact with the outer atmosphere.

4. A multi-layer coated (20) glass (10) according to claim 1, characterized in that the first functional layer (22) and the second functional layer (25) comprise TiOxNy.

5. A multi-layer coated (20) glass (10) according to claim 1, characterized in that the middle dielectric layer (23) comprises at least one or more of ZnAlOx, SiNx, SiOxNy, ZnSnOx, SnOx, TaOx, TaOxNy, TiOx, TiOxNy, TiZrOx, ZrOx, ZrOxNy, SiZrOx, SiZrOxNy, WZrOx, WZrOxNy, NbOx, NbZrOx, MoOx, MoOxNy’ NbZrOx.

6. A multi-layer coated (20) glass (10) according to claim 1, characterized in that it optionally comprises a metallic layer (24).

7. A multi-layer coated (20) glass (10) according to claim 6, characterized in that said metallic layer (24) contacts at least one of the first functional layer (22) and the second functional layer (25).

8. A multi-layer coated (20) glass (10) according to claim 6, characterized in that said metallic layer (24) is at most 10 nm.

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