Coated glass plate

Abstract

To provide an improved transparent glass substrate which offer suitable optical and thermal properties.SOLUTION: A transparent substrate comprises a multi-layer coating stack comprises: (i) n functional metal layers, m; and (ii) n plus 1 (n+1) dielectric layers, d, where the dielectric layers are positioned before and after each functional metal layer; where n is the total number of functional metal layer in the stack counted from the substrate and is greater than or equal to 3; and where each dielectric layer comprises one or more layers. The geometrical layer thickness of each functional metal layer in the multi-layer coating stack, Gm, is greater than the geometrical layer thickness of each functional metal layer appearing before it in the multiple layer coating stack, that is, Gmi+1>Gmi, where i is the position of the functional metal layer in the multi-layer coating stack counted from the substrate.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a substrate having a coating. More specifically, the present invention relates to a transparent substrate having a coating, the coating comprising a plurality of layers, a plurality of which comprise functional layers that reflect solar radiation and / or infrared radiation.

Background Art

[0002] For example, a transparent substrate comprising glass can provide a coating (a "low-emissivity (low-e) coating") that reduces the emissivity of the substrate by reflecting infrared radiation emitted from the interior of a building, for example, when the substrate is installed in a building, for example, in a building, and thus achieves heat insulation properties, and / or a coating (a "solar control coating") that reduces its solar energy transmittance and shields the interior rooms from the ingress of an excessive amount of solar energy (heat).

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[0004] "substrate / base dielectric layer sequence / [silver (Ag) / dielectric layer sequence] b "(where neither the dielectric sequences of a

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[0023] ]The transmittance and reflectivity properties of a vector in the visible region are similar to those released as thermal energy. Energy, that is, the emissivity and solar energy transmittance of the coated glass substrate. By appropriately selecting the material and thickness, the dielectric layer ("DL") can have an effect. Layers can be used.

[0005] Reflection negatively affects the view through the glass substrate. This problem is that through the glass substrate... A clear field of view is especially important for applications where it is crucial for those functions.

[0006] Furthermore, the glass manufacturing industry has expressed interest in the automotive and construction industries due to its thermal insulation properties and desirable low emissivity. Continuing to meet the stringent performance requirements of coated glass substrates for building glazing. There is a demand for this, and as a result, more complex layer sequences (or stacks) are available. It is used to coat glass substrates based on various dielectric materials. In the glass manufacturing industry, the number of dielectric sequences in a coated substrate is 2 or 3. It is becoming more common.

[0007] For example, in International Publication No. 2011 / 020974 (WO2011 / 020974), At least three metallic functional layers and four anti-reflective coatings located on either side of the metallic functional layers It features an alternating array of coatings, and the anti-reflective coating also comprises multiple layers, thin film. A transparent glass substrate having a multilayer structure is described.

[0008] U.S. Patent No. 5,595,825 (US 5,595,825) states that Spectre A film comprising at least three films having reflective properties in the infrared (IR) portion. A stacked coated substrate is disclosed, which offers high selectivity, i.e., T L For a specific value of T, high light transmittance L The ratio of solar transmittance (SF) to (T L / SCIENCE FICTION ) has.

[0009] U.S. Patent Application Publication No. 2013 / 0057951 (US2013 / 005795 1) describes a layer system having an n-functional layer based on, for example, silver and an n+1 dielectric layer. Yes, it is. The absorption layer placed within the stack is extremely important.

[0010] U.S. Patent Application Publication No. 2017 / 0059753 (US2017 / 005975 3) A fill having multiple metallic functional layers (e.g., silver) each having at least one absorption layer. The document also describes the functional layer. The functional layer is surrounded by a phase adjustment layer (dielectric layer).

[0011] Chinese Patent Application Publication No. 102372447 (CN102372447) is a US patent application. Patent Application Publication No. 2017 / 0059753 (US2011 / 0169402) and Similarly, low-emissivity glass containing four silver coating layers for automotive and architectural glass. Although it discloses the specifications of U.S. Patent Application Publication No. 2017 / 0059753 (US20 11 / 0169402) provides specific instructions regarding the relationship between the thickness of the silver layer and the dielectric layer. It does not exist.

[0012] Similarly, the specification of U.S. Patent Application Publication No. 2014 / 0347722 (US2014 / 03 47722), U.S. Patent Application Publication No. 2018 / 0194675 (US2018 / (US Patent Application Publication No. 0194675), and U.S. Patent Application Publication No. 2018 / 0194676 (US (2018 / 0194676) describes a coating layer system having three silver layers. However, none of the literature has taught the relationship between the silver layer and the dielectric layer as specified in this invention. It hasn't been done.

[0013] However, the sputtered dielectric layer is more effective than the sputtered metal layer, such as silver. Because the layer is thick and deposition is slow, the deposition of complex layer sequences onto glass substrates is often difficult. A large number of cathodes are required in industrial coating plants.

[0014] Previously, depositing several complex coating stacks onto a glass substrate required a certain thickness. To achieve a sufficient number of cathodes to deposit the coating material in the desired quantity and order. This was addressed by installing expensive extensions on the coating lines of glass manufacturing plants. It was

[0015] This also allows for the installation of an additional pump section in the extension, enabling multiple reactive deposition processes. It became possible to execute these in order. However, this requires the introduction of necessary engineering. To complete the process, the coating line usually needs to be shut down for an extended period, resulting in significant costs. This is time-consuming and often leads to significant disruption. Each section of the new cathode and pump requires: Power supply, vacuum pump, conveyor section, service and measurement equipment, and control system Integration into the system is also necessary. Such changes often involve the restructuring of downstream logistics. This leads to construction, and in some cases even to new civil engineering works or building expansions. As the requirements for hierarchical and / or more complex stacks become increasingly common, these The problem is set to increase.

[0016] Furthermore, increasing the number of functional metal layers such as silver in the coating sequence results in a coating While the solar protection properties of the substrate can be optimized, increasing the number of functional metallic silver layers can lead to problems with the glass substrate. Light transmittance T of the plate L It will have a negative impact.

[0017] A further effect of increasing the number of layers on the coated substrate is that when viewed from different angles, the coating... The purpose is to bring about a change in the reflection of the outer color of the coating. Therefore, intermediate colors and efficiency In addition to meeting the requirements of the glass industry by providing optimal light transmittance, it also meets the necessary thermal requirements. There is a demand for coated glass substrates that can also provide solar properties. .

[0018] Therefore, the object of the present invention is to provide an improved transparent material that offers appropriate optical and thermal properties. The objective is to provide a clear glass substrate.

[0019] In other words, the present invention can withstand, for example, normal environmental impacts during storage, transportation, and use. This is possible, and provides the necessary substantial intermediate colors and optical properties, with low emissivity (low-e The objective is to provide ) and / or solar-controlled coated glass substrates.

[0020] A further object of the present invention is to provide a coated glass substrate with high selectivity, i.e., good The value is greater than 2.0 (where selectivity = dual glazing unit (DGU) The ratio of light transmittance to g-value, and a low emissivity value corresponding to low sheet resistance, i.e. Preferably less than 3%, and to provide. In the case of double glazing units (DGUs) in a well-maintained building, the coated It is highly desirable for glass to have a uniform color in terms of external reflection. Achieving this is excellent. To achieve an aesthetically pleasing appearance, the color changes of the external reflection of the coated glass substrate are varied. It is important to minimize this when observing within the field of view.

[0021] Because variations in thickness can occur during the manufacturing of coated glass substrates, the building facade To ensure a uniform color appearance, a coated glass substrate is fitted into the two When heavy glazing units are installed on the same unit, the variation in coating thickness is related to the following: Minimizing color variations is extremely important.

[0022] Therefore, in summary, the present invention relates to the prior art processes and products detailed above. Addressing related issues and the optical properties required by the glass industry, such as haze, An economically efficient and commercially desirable coating that meets the requirements of light transmittance and, more importantly, color. The objective is to provide a glass substrate that has been treated with a special coating.

[0023] Therefore, according to the first aspect of the present invention, A transparent substrate comprising a multilayer coating stack, wherein the coating stack is (i) n functional metal layers, m, and (ii) comprising n plus 1 (n+1) dielectric layers, d, wherein the dielectric layers , arranged before and after each functional metal layer, Here, n is the total number of functional metal layers in the stack counted from the substrate, and is 3 or greater. the law of nature, Here, each dielectric layer comprises one or more layers, The geometric layer thickness Gm of each functional metal layer in a multilayer coating stack is determined by the multilayer coating. Greater than the thickness of that geometric layer of each functional metal layer that appears before it in the stack, i.e., That is,[[]] Gm i+1 >Gm i And,[[]] where i is the position of the functional metal layer in the multi-layer coating stack counted from the substrate, and where for each dielectric layer d located before and after each functional metal layer m, the optical layer thickness of each dielectric layer ( opl ) is greater than or equal to the optical layer thickness of the dielectric layer arranged before it in the coating stack ( n )opl ), provided that n-1 Twice the optical layer thickness (opl1) of the first dielectric layer of the coating stack is less than the optical layer thickness (opl2) of the second dielectric layer of the coating stack, i.e., (2xopl1)<opl2, and twice the optical layer thickness (opl ) of the last dielectric layer of the coating stack is greater than the optical layer thickness (opl n+1 ) of the second-to-last dielectric layer, i.e., ( opl n )<(opl pl n )x2, n+1 A transparent substrate comprising a multi-layer coating stack is provided.[[]] That is, for example, in the context of the present invention, when the multi-layer coating stack comprises three silver layers, the optical layer thickness of each dielectric can be expressed as follows.[[]]

[0024] (2xopl1)<opl2≦opl <(opl n n+1 x2)[[]] n+1 where n is 3 and equal to the number of functional metal silver layers.[[]]

[0025] ​When a multilayer coating stack has four silver layers, the thickness of the optical layer of each dielectric is as follows: It can be expressed as follows. (2xopl1) <opl2≦opl3≦opl n <(opl n+1 x2) Here, n is 4, which is equal to the number of functional metallic silver layers.

[0026] When a multilayer coating stack has five silver layers, the thickness of the optical layer of each dielectric is as follows: It can be expressed as follows. (2xopl1) <opl2≦opl3≦opl4≦opl n <(opl n+1 x2) Here, n is 5, which is equal to the number of functional metallic silver layers, and the multilayer coating stack is 6 When a silver layer is present, the thickness of the optical layer of each dielectric can be expressed as follows: (2xopl1) <opl2≦opl3≦opl4≦opl5≦opl n <(opl n +1 x2) Here, n is 5, which is equal to the number of functional metallic silver layers, and so on.

[0027] With respect to a first aspect of the present invention, the functional metal layer may comprise silver or gold, but the functional metal layer may comprise silver It is preferable to include the following.

[0028] The number of functional metal layers in the multilayer coating stack according to the present invention is preferably 3 to 6. May include. More preferably, the number of functional metal layers in the multilayer coating stack is 4 to 6. This includes the number of functional metal layers in the multilayer coating stack. It includes 4.

[0029] Regarding a coating stack for a transparent substrate according to a first aspect of the present invention, each dielectric layer is: TiOx, SnO2, ZnO, ZAO, ZnO:Al, ZrOx, TiOx, Nb2O5 Ta2O5, In2O3, Al2O3, SiO2 or alloys or mixtures thereof, for example. For example, ZnSnOx, InSnOx and / or silicon (oxy) nitride and / or One or more materials selected from luminium (oxy) nitrides and / or alloys thereof It comprises layers. Between the functional metal layer and the subsequent dielectric layer in the coating stack, Ni, C r, W, Nb, Ti, V or alloys and mixtures, for example, NiCr or NiV, An absorption layer is optionally applied, selected from the group containing one or more. The absorption layer is preferably coated It is used to regulate the light and energy transmission of the lighting stack. However, Furthermore, the absorption layer can also be used as a barrier layer.

[0030] In relation to the present invention, the coating stack is a double glazing with Δa*, Δb* ≤ 5 When placed in the unit (DGU), the angle color between 0° and 60° relative to external reflections It is preferable to have a shaft. This is because at all viewing angles up to a maximum of 60°, 0 ° means that the color shift in the field of view is less than 5 for a* and b*.

[0031] More preferably, the coating stack is a double glazing unit with Δb*≦4 ( When placed in the DGU, it has an angular color shift of 0° to 60° for external reflections. Preferably, the coating stack is a double glazing unit with Δa*, Δb* ≤ 3. When placed in (DGU), it has an angular color shift of 0° to 60° for external reflections.

[0032] Furthermore, with respect to the present invention, the coating stack is 5 or less for Δa* and Δb* A thickness variation of 3% (or more) for a single dielectric or metal layer, with a tolerance of 5 or less. When present in a double glazing unit (DGU) accompanied by color, color is affected by external reflections. It is preferable to have a shift. That is, one dielectric or in the coating stack When the metal layer changes the target thickness by 3%, the observed color shift is a* and / or b* is less than 5.

[0033] More preferably, in relation to the present invention, the coating stack is 4 or less with respect to Δa*. , the variation in the thickness of one dielectric or metal layer is 3% (or less) for Δb*, which is 4 or less. When present in a double glazing unit (DGU) as described above, it exhibits a color shift in external reflections. It is preferable to do so.

[0034] Most preferably, in relation to the present invention, the coating stack is 3 or less with respect to Δa*. , the variation in the thickness of one dielectric or metal layer is 3% or less for Δb* (or more) When present in a double glazing unit (DGU) as described above, it exhibits a color shift in external reflections. It is preferable to do so.

[0035] Furthermore, in relation to the first aspect of the present invention, the multilayer coating stack is The first dielectric layer, d1, The first functional metal layer m1, The second dielectric layer, d2, The second functional metal layer m2, The third dielectric layer, d3, The third functional metal layer m3, The fourth dielectric layer, d4, A transparent substrate can be provided that has the following features.

[0036] In relation to this embodiment of the first aspect of the present invention, the first, second, and third functional metal layers Each may have a layer of silver.

[0037] Furthermore, in relation to this embodiment of the first aspect of the present invention, the first induction closest to the glass substrate The electrochemical layer d1 may consist of layers based on titanium (Ti) oxide in sequence, starting from the glass substrate. Therefore, the first dielectric layer d1 closest to the glass substrate is titanium (Ti) from the glass substrate. It may subsequently comprise a layer based on an oxide of and / or a layer based on an oxide of zinc (Zn).

[0038] Furthermore, the second dielectric layer d2 is made up of a layer based on zinc oxide, and a sub-dielectric layer, derived from the glass substrate. It may comprise layers based on lead (Zn) and tin (Sn) oxides in sequence.

[0039] The third dielectric layer d3 is preferably made from a glass substrate and based on zinc (Zn) oxide. It may comprise a layer and / or a layer based on zinc (Zn) and tin (Sn) oxides in sequence. The third dielectric is also a layer based on zirconium (Zr) oxide, and / or It may also include a layer based on tan oxide. The third dielectric layer is a layer based on titanium oxide. It may further comprise a layer based on zinc oxide located above it.

[0040] An absorption layer of NiCr may also be provided between the third metal layer and the fourth dielectric layer sequence. The NiCr layer is preferably used to adjust the light transmittance of the multilayer coating stack. It may be provided.

[0041] As a result, the multilayer coating stack is preferably, The first dielectric layer, d1, The first functional metal layer m1, The second dielectric layer, d2, The second functional metal layer m2, The third dielectric layer, d3, The third functional metal layer m3, Absorbing layer a1, The fourth dielectric layer d4, It can be equipped with.

[0042] Furthermore, the fourth dielectric layer is a layer based on zinc (Zn) oxide, and / or zinc ( It may comprise layers based on oxides of Zn (Zn) and tin (Sn).

[0043] Furthermore, in relation to the first aspect of the present invention, a multilayer coating stack is The first dielectric layer, d1, The first functional metal layer m1, The second dielectric layer, d2, The second functional metal layer m2, The third dielectric layer, d3, The third functional metal layer m3, The fourth dielectric layer d4, The fourth functional metal layer m4, The fifth dielectric layer d5, A transparent substrate with the following features can be provided.

[0044] In relation to this embodiment of the first aspect of the present invention, the first, second, third and fourth functional metals The genera may contain layers of silver.

[0045] Furthermore, the first, second, third, and fourth dielectric layers may be as described above, and the fifth dielectric layer This is a layer based on zinc (Zn) oxide, and / or zinc (Zn) and tin (Sn) It may have a layer based on an oxide.

[0046] An absorption layer of NiCr may also be provided between the third metal layer and the fourth dielectric layer sequence. The NiCr layer is preferably used to adjust the light transmittance of the multilayer coating stack. It may be provided. Similarly, between the fourth metal layer and the fifth dielectric layer sequence, NiCr An absorption layer may also be provided.

[0047] As a result, the multilayer coating stack is preferably, The first dielectric layer, d1, The first functional metal layer m1, The second dielectric layer, d2, The second functional metal layer m2, The third dielectric layer, d3, The third functional metal layer m3, Absorbing layer a1, The fourth dielectric layer d4, The fourth functional metal layer m4, Absorption layer a2 and, The fifth dielectric layer d5, It can be equipped with.

[0048] Furthermore, in relation to the first aspect of the present invention, each functional metal layer has a thickness of 5 to 25 nm. Obtain. More preferably, each functional metal layer may have a thickness of 6 to 23 nm. Most preferably Each functional metal layer may have a thickness between 8 and 21 nm.

[0049] Preferably, with respect to the first aspect of the present invention, the first dielectric layer d1 is made from a glass substrate, A layer based on titanium (Ti) oxide, and / or a layer based on zinc (Zn) oxide Prepare in order.

[0050] Furthermore, in relation to the first aspect of the present invention, the second, third, fourth and fifth dielectric layers d2, d3, d4, and d5 are preferably from a glass substrate, respectively. (i) A layer based on zinc (Zn) oxide and / or an absorption layer based on NiCr; Beauty (ii) Oxides of zinc (Zn) and tin (Sn), and / or acids of tin (Sn) Layers based on monsters, They can prepare in order.

[0051] NiCr-based absorption layers can also be present in the coating stack. The coating is preferably in direct contact with the functional metal layer and is a layer based on zinc (Zn) oxide. It can be used fairly often.

[0052] The third dielectric layer d3 may also preferably include a layer based on titanium (Ti) oxide.

[0053] The fifth dielectric layer d5 may further comprise a layer based on zirconium (Zr) oxide.

[0054] Furthermore, with respect to the first aspect of the present invention, the thickness of the optical layer of the first dielectric layer d1 is preferably The range is 30-70 nm. The thickness of the optical layer is the refractive index of the material (measured at a wavelength of 550 nm). It is equal to the product of the (value) and the geometric layer thickness of the material.

[0055] That is, with respect to the first aspect of the present invention, the thickness of the first dielectric layer d1 is twice the thickness of the optical layer. Preferably, the thickness of the optical layer of the second dielectric layer is less than d2, i.e., (2xd1) <d2である。

[0056] The thickness of the optical layer of the second dielectric layer d2 is preferably in the range of 60 to 180 nm. Furthermore, the thickness d2 of the optical layer of the second dielectric layer is preferably the thickness of the optical layer of the third dielectric layer. d is less than or equal to d3, that is, d2 ≤ d3.

[0057] The thickness of the optical layer of the third dielectric layer d3 is preferably in the range of 70 to 200 nm. Furthermore, the thickness d3 of the optical layer of the third dielectric layer is preferably the thickness of the optical layer of the fourth dielectric layer. d is less than or equal to d4, that is, d3 ≤ d4.

[0058] The thickness of the optical layer of the fourth dielectric layer d4 is preferably in the range of 80 to 220 nm. The thickness of the optical layer of dielectric layer d5 is preferably in the range of 45 to 120 nm.

[0059] In other words, with respect to the first aspect of the present invention, the thickness of the optical layer of the fourth dielectric layer d4 is preferably Alternatively, the fifth dielectric layer d5 is less than twice the thickness of the optical layer, i.e., d4 < (2xd5) be.

[0060] According to a second aspect of the present invention, the multilayer coating stack according to the first aspect of the present invention is A double glazing unit incorporating a transparent substrate is provided. All of the above features regarding transparent substrates and multilayer coating stacks by [Name of Manufacturer / Company] are as described above. It is also preferable to apply this to a double glazing unit according to the second embodiment of the present invention.

[0061] In the first and second aspects of the present invention, it is preferable that the transparent substrate comprises glass. It is more preferable to have float glass.

[0062] Furthermore, with respect to a double glazing unit according to a second aspect of the present invention, double glazing The glazing unit may have a selectivity of 1.9 or higher. More preferably, the glazing unit The selectivity of the glazing unit is 2.0 or higher. Most preferably, the selectivity of the glazing unit is 2.1 or higher. Selectivity is determined by the light transmittance and g-value of the double glazing unit (DGU). This is the ratio to the total energy transmittance. Light transmittance and g-value are incorporated herein by reference. It is calculated according to the standard EN 410.

[0063] Furthermore, regarding the double glazing unit according to the second aspect of the present invention, double glazing The number of units is preferably 5 or less, more preferably 4.0 or less, and most preferably 3. This shows the angular dependence of a* and b* external reflections from 0° to 60°, including values ​​less than or equal to 0.

[0064] Furthermore, the double glazing unit according to the second aspect of the present invention preferably has 5 or fewer. More preferably 4.0 or less, most preferably 3.0 or less, with a thickness of 3% per layer. It also features a color shift that involves subtle variations. [Brief explanation of the drawing]

[0065] Herein, embodiments of the present invention will be described with reference to Figures 1 to 5 below, as non-limiting examples. This will be explained in the specifications.

[0066] [Figure 1] This is a cross-sectional view of a double glazing unit. [Figure 2] This graph shows the angular dependence (in degrees) of external reflection between a standard double glazing unit (DGU) and b*, created with glass coated according to Example 1. [Figure 3] This graph shows the angular dependence (in degrees) of external reflection between a standard double glazing unit (DGU) and b*, created with glass coated according to Example 2. [Figure 4] This graph shows the angular dependence (in degrees) of external reflection between a standard double glazing unit (DGU) and a*, created with glass coated according to Example 3. [Figure 5] This graph shows the angular dependence (in degrees) of external reflection between a standard double glazing unit (DGU) and a*, created with glass coated according to Example 4.

[0067] In Figures 2 and 3, b* represents the color change from blue to yellow in the CIELAB color space. In Figures 4 and 5, a* represents the color change from green to red in the CIELAB color space. [Modes for carrying out the invention]

[0068] Details are shown in Table 1. In the following example, AC and / or DC magnetrons (or pulsed Using a DC sputtering device, apply medium-frequency sputtering as needed. The coating is then deposited onto a standard 6mm thick float glass plate with a light transmittance range of 90%. did. The dielectric layers of zinc (Zn) and tin (Sn) oxides are argon / oxygen (Ar / O2) In a sputtering atmosphere, a zinc-tin target (weight ratio Zn:Sn approximately 50:50) reacts It was sputtered. Titanium oxide (TiO x The layer is made of metallic titanium (Ti) or conductive titanium oxide (TiO x The material was deposited from the target in an argon / oxygen (Ar / O2) sputtering atmosphere. The ZnO:Al growth-promoting layer is formed in an Ar / O2 sputtering atmosphere using an Al-doped zinc metal target. It was sputtered from a tuff (aluminum (Al) content of approximately 2% by weight). In all examples, the functional layer, consisting of virtually pure silver (Ag), does not contain added oxygen and residual oxygen. The pressure is 10 -4 Sputtering from a silver target in an argon (Ar) sputtering atmosphere of less than mbar I was defeated. The barrier layer of Al-doped zinc oxide, also known as ZAO, located above the silver-based functional layer, In a pure argon (Ar) sputtering atmosphere without oxygen addition, a conductive oxide target is used. ZnO x : Sputtered from an Al target. A layer of NiCr located directly above the silver-based functional layer (as an absorption layer and / or barrier layer) (Possible to function) Sputtering from a metal NiCr target in a pure argon sputtering atmosphere It was done.

[0069] [Table 1]

[0070] Table 1 shows the comparative coated glass plate and the layer thickness of the coated glass plate according to the present invention. Details of Kens, light transmittance (T L ), g value, selectivity, color temperature during angle measurement from 0° to 60° Observation of the color shift Δa*, Δb* when the thickness variation is 3%. The results for each layer sequence from the point are provided. All values ​​are from a double glazing unit. This is the value of DGU. The color shift is always the shift of external reflection. For each example, The layers begin with the top layer of each row and are deposited on a 6mm float glass plate in the order shown. It was done.

[0071] Color Characteristics - The color characteristics of each sample are based on established CIE LAB L*, a*, and b* coordinates. Measured and reported using (for example, International Publication No. 20, which is incorporated by reference herein) (As described in paragraphs

[0030] and

[0031] of issue 04 / 063111 (WO2004 / 063111A1).

[0072] In the following example, where the thickness of the optical layer of the coating is provided, the thickness of the optical layer is TiOx The refractive index values ​​are 2.45 for ZnO:Al, 2.07 for ZAO, and the refractive index of ZnSnOx. It is determined using the rate 2.07. [Examples]

[0073] (Example 1) The coating sequence described in Example 1 was prepared as follows: 6 mm flow On a glass plate, the first titanium oxide (TiO) x By applying a layer, the thickness of the optical layer is 46.6 nm. A first dielectric coating sequence having opl1 was formed. Next, titanium oxide (TiO x ) A layer of aluminum-doped zinc oxide (Z) with an optical thickness of 7.3 nm is placed on top of the layer. A layer of nO:Al was applied. As a result, the first dielectric layer had an optical thickness of 53.9 nm. It is formed with opl1. Next, the first silver functional layer (Ag layer 1) is placed on top of the ZnO:Al layer. The coating was applied until it reached a thickness of 9.3 nm. Next, the optical layer thickness was reduced to 4.1 nm. The aluminum-doped zinc oxide (ZAO) barrier layer is the first silver functional layer (Ag layer 1). Subsequent tin and zinc oxide layers were deposited on top, applying an optical layer thickness of 136.6 nm. ZnSnO x The first silver functional layer was protected from the second coating layer sequence of ). As a result, the combined optical layer thickness OPL2 is 140.7 nm, made of tin and phosphate oxide. Lead (ZnSnO x A second induction comprising a layer of ) and aluminum-doped zinc oxide (ZAO) An electrolytic layer sequence was formed. Next, a second silver functional layer (Ag layer 2) was added to a thickness of 11.5 nm. Then it was applied above the second dielectric layer. This was then applied to an aluminum layer with an optical layer thickness of 4.1 nm. A second barrier layer of nium-doped zinc oxide (ZAO) follows, and then a second silver functional layer (Ag layer) is formed. 2) was applied above. Next, a second barrier of aluminum-doped zinc oxide (ZAO) The layer has an optical layer thickness of 64.2 nm and is made of tin and zinc oxide (ZnSnO x ) the second invitation It was coated with an electrochemical coating layer. Second titanium oxide (TiOx ) Apply the layer, A coating with an optical layer thickness of 71.1 nm was formed. Second aluminum-doped oxidation Zinc (ZnO:Al) is coated onto titanium oxide to an optical thickness of 7.3 nm, and aluminum A layer of nium-doped zinc oxide (ZAO), tin, and zinc oxide (ZnSnO) x ) layer, oxidation Titanium (TiO x Formed from a layer of aluminum-doped zinc oxide (ZnO:Al). Furthermore, a third dielectric layer sequence, comprising an optical layer thickness of 146.7 nm (OPL3), was completed. Next, a third silver functional layer (A) with a thickness of 15.6 nm is placed above the third dielectric layer sequence. A g layer (3) was applied. Again, an aluminum-doped oxide layer with an optical layer thickness of 4.1 nm was applied. A zinc (ZAO) layer is applied on top of the third silver functional layer (Ag layer 3), and aluminum doping is performed. Above the third layer of zinc oxide (ZAO), there is an optical layer with a thickness of 159.4 nm containing tin and oxide. The third layer of zinc (ZnSnO x ) Applying this, the combined optical layer thickness OPL4 is 163 A fourth dielectric layer sequence of 0.5 nm thickness was formed. Next, a fourth silver layer sequence of 17.4 nm thickness was formed. The active layer (Ag layer 4) is made of tin and zinc oxide (ZnSnO x Applied to the upper part of the third layer of ) Again, a layer of aluminum-doped zinc oxide (ZAO) with an optical layer thickness of 4.1 nm was added. It was deposited above the silver functional layer (Ag layer 4). Finally, the optical layer had a thickness of 82.8 nm. The fourth layer (ZnSnO) consists of zinc oxide and zinc oxide. x ) is aluminum-doped zinc oxide (ZAO) Applied above the fourth layer, it has a combined optical layer thickness of 86.9 nm, OPL5. The fifth dielectric sequence has been completed. Therefore, the layer sequence represented by, for example, 1, is The thickness of the optical layer and the geometric layer of the silver functional layer can be expressed as follows: Glass / TiO x , opl=46.6nm / ZnO:Al, opl=7.3nm / Ag 19.3nm / ZAO, opl=4.1nm / ZnSnO x , opl=136.6nm / Ag211.5nm / ZAO, opl=4.1nm / ZnSnO x , opl=64. 2nm / TiO x , opl=71,1nm / ZnO:Al, opl=7.3nm / Ag3 15.6 nm / ZAO, opl=4.1 nm / ZnSnO x 159.4nm / Ag4 17.4 nm / ZAO, opl=4.1 nm / ZnSnO x , opl=82.8nm.

[0074] The "opl" value expressed in relation to the above and below examples represents the thickness of the optical layer of the material. Based on the product of the refractive index of the material and the geometric layer thickness of the material measured at a wavelength of 550 nm. ru.

[0075] The thickness of each optical layer in the five dielectric layer sequence op11 to opl5 is as follows: It can be summarized as follows. opl1=53.9nm, opl2=140.7nm, opl3=146.7nm, o pl4 = 163.5 nm, opl5 = 86.9 nm.

[0076] Furthermore, with respect to Example 1, the thickness of each silver functional layer dAg is the silver functional layer up to the glass substrate. It increases as the distance increases. That is, for example, the thickness of the second silver functional layer dAg2 is This is greater than the thickness of the first silver functional layer dAg1.

[0077] As a result, with respect to Example 1, according to the present invention, the following relationship exists: (i) Regarding the thickness of the silver functional layer, dAg1 <dAg2<dAg3<dAg4、 (ii) The combined dielectric layer sequence before, after, and between each silver functional layer Regarding thickness, (opl1x2) <opl2<opl3<opl4<(opl5x2) The condition is met.

[0078] The double glazing unit (DGU) 1 shown in Figure 1 is coated as shown in Example 1. The preparation was carried out using a 6mm glass sheet 2 equipped with 5, as detailed in Example 1. A 6mm thick float glass sheet 2 with a coating like this is placed on a second 4mm thick sheet. Assembled with 3 uncoated float glass sheets. 2 glass sheets 2 and 3 are the coated side 5 of the coated glass sheet 2 facing the gap 8. It was assembled in such a way (referred to as DGU position 2 during installation). That is, coating The coated glass sheet 2 is more susceptible to external environmental influences than the uncoated glass sheet 3. It is close to 0, forming an insulating double glazing unit. The glass sheets are 1 between them. They are placed with a gap distance of 6 mm, and the gap 8 contains 90% argon gas and 1 It was filled with 0% air. Therefore, the coating of the coated glass sheet 2 The uncoated surface 4 is located at position 1, and the two coatings of the second glass sheet 3 The untreated faces 6 and 7 were located at positions 3 and 4, respectively. A low-e cone was located at position 2. The properties of the coated double glazing were measured according to EN 410. The results were This is shown in Table 2.

[0079] [Table 2]

[0080] In Table 2, the selectivity value is equal to the ratio of the light transmittance to the g-value of the double glazing unit. Furthermore, each value is calculated using EN410, which is incorporated herein by reference.

[0081] The difference in external reflection of the DGU prepared with the coating of Example 1 according to the present invention is a* Regarding b*, for field angles of 0° and 60°, Δa* = 1.0 and Δb* = 2 It was found to be 0.9. Figure 2 shows a graph of the change in b* relative to the field of view for Example 1. This indicates that the coating used in Example 1 is within the required limits.

[0082] Furthermore, with respect to the DGU prepared with the coating of Example 1 according to the present invention, the thickness is 3%. The cases with a change in color shift are Δa*=2.5 and Δb=*2.8. The values ​​of Δa* and Δb* of DGU prepared using the coating according to the present invention are The permissible limit is within 5, preferably within 4, and particularly preferably the limit is It is within 3.

[0083] (Comparative Example 2) The coating sequence described in Example 2 was prepared as follows: 6 mm float On a glass plate, the first titanium oxide (TiO x By applying a layer, the thickness of the optical layer is 80.9 nm. The first dielectric coating sequence opl1 was formed. Next, titanium oxide (TiO x A first silver functional layer (Ag layer 1) was applied to the ) layer to a coating thickness of 14 nm. Next, aluminum-doped zinc oxide (ZAO) with an optical layer thickness of 4.1 nm The rear layer is deposited on the first silver functional layer (Ag layer 1), and the first silver functional layer is made of 151.1n The subsequent application of tin and zinc oxide (ZnSnO) with an optical layer thickness of m x ) the second It was protected from the coating layer sequence. As a result, the combined optical layer thickness was 155. 2nm, tin and zinc oxide (ZnSnO x ) layer and aluminum-doped zinc oxide (Z A second dielectric layer sequence comprising AO) was formed. Next, a second silver functional layer (Ag layer) was formed. 2) was applied to the top of the second dielectric layer with a thickness of 14 nm. Then the second silver machine was applied to it again. Aluminum with an optical layer thickness of 4.1 nm applied above the functional layer (Ag layer 2). A second barrier layer of doped zinc oxide (ZAO) follows. Next is aluminum-doped zinc oxide. The second barrier layer of (ZAO) is made of tin and phosphate oxide with an optical layer thickness of 78.7 nm. Lead (ZnSnO x The second dielectric coating layer of ) was used. n(TiO x ) Apply a layer to form a coating with an optical layer thickness of 73.5 nm, 1 Aluminum-doped zinc oxide (ZA) with a combined optical layer thickness of 56.3 nm A layer of O, tin and zinc oxide (ZnSnO) x ) layer, and titanium oxide (TiO x ) The third dielectric layer sequence opl3, formed from the layers, was completed. Next, the third dielectric A third silver functional layer (Ag layer 3) with a thickness of 14 nm was applied above the body layer sequence. A third layer of aluminum-doped zinc oxide (ZAO) with an optical layer thickness of 4.1 nm is used. Applied on top of the silver functional layer (Ag layer 3), the third layer of aluminum-doped zinc oxide (ZAO) Above it, tin and zinc oxide (ZnSnOx) with an optical layer thickness of 130.4 nm A third layer is applied to create a fourth dielectric layer having a combined optical layer thickness of 134.6 nm. Sequence opl4 was formed. Next, a fourth silver functional layer (Ag layer 4) with a thickness of 14 nm was formed. Tin and zinc oxide (ZnSnO) x It was applied to the upper part of the third layer of the optical layer. Again, the thickness of the optical layer This forms a 4.1 nm aluminum-doped zinc oxide (ZAO) layer, and a fourth silver functional layer (Ag layer). 4) was deposited on top of the coating. Finally, the optical layer had a thickness of 76.6 nm of tin. The fourth layer of zinc oxide (ZnSnO x ) is the first of aluminum-doped zinc oxide (ZAO) A fifth dielectric is applied above layer 4, having a combined optical layer thickness of 80.7 nm. I completed sequence opl5.

[0084] Therefore, the layer sequence in Example 2 can be expressed as follows: Glass / TiO x , opl=80.9nm / Ag 14nm / ZAO, opl=4.1 nm / ZnSnO x , opl=151.2nm / Ag 14nm / ZAO, opl=4. 1nm / ZnSnO x opl=78.7nm / TiO x opl=73.5nm / Ag 14nm / ZAO, opl=4.1nm / ZnSnO x 130.4nm / Ag 14 nm / ZAO, opl=4.1nm / ZnSnO x , opl=76.6nm

[0085] Each optical layer of the five dielectric layer sequences op1 to opl5 in Comparative Example 2 The thickness can be summarized as follows: opl1=80.9nm, opl2=155.2nm, opl3=156.3nm, o pl4 = 134.5 nm, opl5 = 80.7 nm

[0086] Therefore, in the case of Comparative Example 2, the following relationship regarding the thickness of the silver functional layer is not satisfied. dAg1 <dAg2<dAg3<dAg4

[0087] Instead, the following relationship exists regarding the thickness of the silver functional layer in Comparative Example 2. dAg1=dAg2=dAg3=dAg4 In other words, the thickness of each silver functional layer is the same for all layers.

[0088] Furthermore, in the case of Comparative Example 2, the dielectrics before, after, and between each silver functional layer were combined. The following relationship determines the thickness of the layer sequence. (opl1x2) <opl2<opl3<opl4<(opl5x2) This condition is not met, and instead, twice the optical thickness of the first dielectric layer (opl1x2) is used. The optical thickness of the second dielectric layer OPL2 is greater than the optical thickness of the combined optical thickness layer OPL 3 is greater than the combined optical thickness layer OPL4.

[0089] Therefore, in the case of Comparative Example 2, the following relationship exists between the thicknesses of the combined optical layers. . (opl1x2)>opl2 <opl3>opl4<(opl5x2)

[0090] A double glazing unit (DGU) 1 as shown in Figure 1 is compared to the one described in Comparative Example 2. It was prepared using a 6 mm glass sheet 2 having a coating 5. That is, A 6mm thick float glass sheet 2 with a coating as detailed in Example 2, Assembled with a second 4mm thick uncoated float glass sheet 3. The two sheets of glass 2 and 3 have coated sides 5 between them. It is assembled to face gap 8 (referred to as position 2 of the DGU during installation), and the coating The coated glass sheet 2 is more effective against external elements than the uncoated glass sheet 3. Near boundary 10, it forms an insulated double glazing unit. The glass sheets are between them. They are placed with a gap distance of 16 mm, and the gap 8 is 90% argon gas. It was filled with 10% air. Therefore, the coated glass sheet 2 The uncoated surface 4 is located at position 1, and the two coatings of the second glass sheet 3 The untreated surfaces 6 and 7 were located at positions 3 and 4, respectively. Comparative Example 2, position 2 The properties of the double glazing with low-e coating were measured according to EN410. The results are shown in Table 3.

[0091] [Table 3]

[0092] In Table 3, the selectivity value is equal to the ratio of the light transmittance to the g value of the double glazing unit. Each value is calculated using EN410, which is incorporated herein by reference.

[0093] According to Comparative Example 2, D was prepared with coatings for viewing angles of 0° and 60°. The difference in external reflections of the GU is Δa*=3.9 and Δb*=9.4 with respect to a* and b*. It was found that this was the case. Figure 3 shows a graph of the change in b* relative to the field of view for Example 2.

[0094] Furthermore, regarding the DGU prepared with the coating of Example 2 (not according to the present invention) The color shift with a 3% thickness change is as follows: Δa*=6.2 and Δb*=8.0 Yes, that is, Δa* and Δ of the DGU using the coating detailed in Comparative Example 2. The value of b* far exceeds the acceptable limit of 5.

[0095] (Example 3) The coating sequence described in Comparative Example 3 was prepared as follows: 6 mm flow On a glass plate, the first titanium oxide (TiO) x By applying a layer, the thickness of the optical layer is 53.9 nm. A first dielectric coating sequence having opl1 was formed. Next, titanium oxide (TiO x A first silver functional layer (Ag layer 1) is coated on top of the ) layer with a coating thickness of 11.3 nm. Next, an aluminum-doped zinc oxide (ZAO) with an optical layer thickness of 4.1 nm was applied. The barrier layer is deposited on the first silver functional layer (Ag layer 1), and the first silver functional layer is 165. The subsequent tin and zinc oxide (ZnSnOx) second optical layer was applied with a thickness of 6 nm. The coating layer sequence was protected. As a result, the combined light at 169.7 nm A layer of tin and zinc oxide (ZnSnOx) with a thickness of 2 and aluminum A second dielectric layer sequence was formed, comprising a layer of zinc oxide (ZAO). Next, A second silver functional layer (Ag layer 2) was applied above the second dielectric layer with a thickness of 14.6 nm. In addition, an aluminum-doped zinc oxide (ZAO) with an optical layer thickness of 4.1 nm is used. A second barrier layer followed again, applied above the second silver functional layer (Ag layer 2). Next, Al A second barrier layer of zinc oxide (ZAO) with an optical layer thickness of 51.8 nm is applied. And tin and zinc oxide (ZnSnO x ) coated with a second dielectric coating layer The second titanium dioxide (TiO) x ) Applying a layer, the optical layer thickness is 80.9 nm. Forming a coating, a layer of aluminum-doped zinc oxide (ZAO), tin and zinc oxide ( ZnSnO x ) layer, titanium dioxide (TiO x ) formed from a layer of 136.8nm light The third dielectric layer sequence, having a thickness of opl3, was completed. Next, the third dielectric... A third silver functional layer (Ag layer 3) with a thickness of 15 nm was applied above the body layer sequence. A layer of aluminum-doped zinc oxide (ZAO) with an optical layer thickness of 4.1 nm is used. Applied to the silver functional layer (Ag layer 3), aluminum-doped zinc oxide (ZAO) 3 Above the layer is a third layer of tin and zinc oxide (ZnSnO) with an optical layer thickness of 128.3 nm. x ) is applied, and the thickness of the combined optical layer OPL4 is 132.4 nm, which is the fourth dielectric A layer sequence was formed. Next, a fourth silver functional layer (Ag layer 4) with a thickness of 15.5 nm was added. Tin and zinc oxide (ZnSnO) x It was applied to the upper part of the third layer of the optical layer. Again, the thickness of the optical layer The fourth is coated with a 4.1 nm aluminum-doped zinc oxide (ZAO) layer. It was deposited above the silver functional layer (Ag layer 4). Finally, the tin optical layer had a thickness of 31.1 nm. and the fourth layer of zinc oxide (ZnSnO x ) is aluminum-doped zinc oxide (ZAO) Applied above the fourth layer, the combined optical layer has a thickness of 35.2 nm, OPL5. The 5 dielectric sequence has been completed.

[0096] Therefore, the layer sequence of Comparative Example 3 can be expressed as follows. Glass / TiO x , opl=53.9nm / Ag 11.3nm / ZAO, opl=4. 1nm / ZnSnO x , opl=165.6nm / Ag 14.6nm / ZAO, opl =4.1nm / ZnSnO x opl=51.8nm / TiO x , opl=80.9nm / Ag 15nm / ZAO, opl=4.1nm / ZnSnO x 128.3nm / Ag 15.5nm / ZAO, opl=4.1nm / ZnSnO x , opl = 31.1 nm.

[0097] The combined optics for each of the five dielectric layer sequences op11 to opl5 The thickness of the layers can be summarized as follows: opl1=53.9nm, opl2=169.7nm, opl3=136.8nm, o pl4 = 132.4 nm, opl5 = 35.2 nm

[0098] Regarding the functional layers of silver, the following relationship exists: dAg1 <dAg2<dAg3<dAg4

[0099] However, the combined dielectric layer sequence before, after, and between each silver functional layer Regarding the thickness of the lance, the relationship observed in Example 1 is, (opl1x2) <opl2<opl3<opl4<(opl5x2) This is not satisfied in Comparative Example 3, but instead, the second dielectric sequence layer op12 The combined optical thickness is less than twice the combined optical thickness layer op11, and The combined optical thickness layer OPL2 is larger than the combined optical thickness layer OPL3. The combined optical thickness layer OPL3 is larger than the combined optical thickness layer OPL4. That is, for Comparative Example 3, the combined optical thickness layer thicknesses were from op11 to opl5 The following relationship is observed: (opl1x2)>opl2>opl3>opl4<(opl5x2)

[0100] The double glazing unit (DGU) 1 shown in Figure 1 is coated as shown in Comparative Example 3. The adjustment was made using a 6mm glass sheet 2 equipped with a 5mm element, as detailed in Example 3. A 6mm thick float glass sheet 2 with a coating like this is placed on a second 4mm thick sheet. Assembled with 3 uncoated float glass sheets. 2 glass sheets 2 and 3 are the coated side 5 of the coated glass sheet 3 facing the gap 8. It was assembled in such a way (referred to as DGU position 2 during installation). That is, coating The coated glass sheet 5 is more effective against external environments than the uncoated glass sheet 3. It is close to 0, forming an insulating double glazing unit. The glass sheets are 1 between them. They are placed with a gap distance of 6 mm, and the space gap 8 contains 90% argon gas and 1 It was filled with 0% air. Therefore, the coating of the coated glass sheet 2 The uncoated surface 4 is located at position 1, and the two coatings of the second glass sheet 3 The non-coated surfaces 6 and 7 were present at positions 3 and 4, respectively. At position 2 of Comparative Example 3, l The properties of the double glazing with a low-e coating were measured according to EN 410 and the results are as shown in Table 4.

[0101]

Table 4

[0102] In Table 4, the selectivity value is equal to the ratio of the light transmittance to the g-value of the double glazing unit, and each value is calculated using EN410 incorporated herein by reference.

[0103] For the DGU prepared by coating according to Comparative Example 3, when the viewing angles are 0° and 60°, the differences in external reflection for a* and b* were found to be Δa* = 12.1 and Δb* = 1.7. The graphical representation of the change in a* versus the viewing angle for Example 3 is shown in FIG. 4.

[0104]

[0105] For the DGU prepared with the coating described in Comparative Example 3, the color shift with a 3% thickness change is for Δa* = 10.6 and Δb* = 3.2. That is, the value of Δa* for the DGU using the coating described in detail in Comparative Example 3 far exceeds the tolerance limit of 5.

[0105] (Example 4) The coating sequence described in Example 4 was prepared as follows. On a 6 mm float glass plate, a first titanium oxide (TiO ) layer was applied to form a first dielectric coating sequence having an optical layer thickness of 55.1 nm o x pl1. Next, titanium oxide (T iO iO x On top of the ) layer, a first silver functional layer (Ag layer 1) is applied with a coating thickness of 8.9 nm. Next, a burr of aluminum-doped zinc oxide (ZAO) with an optical layer thickness of 4.1 nm was used. The A layer is deposited on the first silver functional layer (Ag layer 1), and the first silver functional layer is 132.5 nm The subsequent second coating of tin and zinc oxide (ZnSnOx) was applied with the thickness of the optical layer. It was protected from the ting layer sequence. As a result, the combined optical layer of 136.6 nm A layer of tin and zinc oxide (ZnSnOx) with a thickness of 0.2 and aluminum-doped acid A second dielectric layer sequence comprising zinc oxide (ZAO) was formed. Next, the second silver machine An optical layer (Ag layer 2) was applied to the top of the second dielectric layer with a thickness of 12 nm. A second barrier layer of aluminum-doped zinc oxide (ZAO) with a thickness of 4.1 nm. This was followed again, and applied to the top of an additional silver functional layer (Ag layer 2). Next, aluminum do A layer of zinc oxide (ZAO) is layered with a layer of tin and zinc oxide (ZnSnOx) at 68.3 nm. It was coated to a thickness of 74.7 nm. Next, titanium oxide (TiO) was applied. x ) layer The applied third dielectric layer sequence has a combined optical layer thickness of 147.1 nm. OPL3 was formed. Next, a 14.5 nm thick third dielectric layer was placed above the third dielectric layer sequence. A silver functional layer (Ag layer 3) was applied. Next, a coating that reduces the permeability of the silver layer was applied to the silver layer. Therefore, a nickel-chromium absorption layer with a thickness of 0.3 nm was applied. The thickness of the optical layer was 163. 5nm third layer of tin and zinc oxide (ZnSnO x ) is placed above the NiCr layer, and the combination The combined optical layer thickness OPL4 forms a fourth dielectric layer sequence of 163.5 nm. Next, a fourth silver functional layer (Ag layer 4) with a thickness of 16.9 nm was added, along with tin and zinc oxide (Z nSnO x It was applied to the upper part of the third layer of the optical layer, which was 0.8 nm thick nickel. A layer of chromium was applied above the fourth silver layer. Finally, the thickness of the optical layer was 84.9 nm. The fourth layer (ZnSnO) consists of zinc oxide and zinc oxide. x ) applied to the combined effect of 86.9nm We have completed a fifth dielectric sequence with an effective optical layer thickness of 0PL5.

[0106] Therefore, for example, the layer sequence represented by 1 has a thickness and geometry of the optical layer of the silver functional layer. The thickness of the academic layer can be expressed as follows: Glass / TiO x , opl=55.1nm / Ag 8.9nm / ZAO, opl=4. 1nm / ZnSnO x ,opl=132.5nm / Ag 12nm / ZAO,opl= 4.1nm / ZnSnO x opl=68.3nm / TiO x , opl=74.7nm / Ag 14.5nm / NiCr 0.3nm / ZnSnO x 163.5nm / Ag 1 6.9nm / NiCr 0.8nm / ZnSnO x , opl = 84.9nm.

[0107] The thickness of each optical layer in the five dielectric layer sequence op11 to opl5 is as follows: It can be summarized as follows. opl1=55.1nm, opl2=136.6nm, opl3=147.1nm, o pl4 = 163.5 nm, opl5 = 84.9 nm. Furthermore, regarding Example 4, the thickness dAg of each silver functional layer is the distance of the silver functional layer to the glass substrate. Increases as it increases. That is, for example, the thickness of the second silver functional layer dAg2 is greater than the thickness of the first silver functional layer dAg1.

[0108] As a result, for Example 4 according to the present invention, the following relationships are satisfied. (i) Regarding the thickness of the silver functional layer, dAg1 < dAg2 < dAg3 < dAg4 (ii) Regarding the thickness of the combined dielectric layer sequences before, after, and between each silver functional layer it is (opl1x2) < opl2 < opl3 < opl4 < (opl5x2).

[0109] The double glazing unit (DGU) 1 shown in FIG. 1 was adjusted using a 6 mm glass sheet 2 provided with a coating 5 as shown in Example 4. That is, as detailed in Example 4 a 6 mm thick float glass sheet 2 with the coating applied was assembled with a second 4 mm thick uncoated float glass sheet 3. The two glass sheets 2, 3 were assembled such that the coated side 5 of the coated glass sheet faced the gap 8 (referred to as position 2 of the DGU during installation). That is, the coated glass sheet 5 was closer to the external environment 10 than the uncoated glass sheet 3, forming a heat-insulating double glazing unit. The glass sheets were arranged with a 16 mm gap distance between them, and the gap 8 was filled with 90% argon gas and 10% air filling. Thus, the uncoated surface 4 of the coated glass sheet 2 was at position 1, and the two uncoated surfaces 6 and 7 of the second glass sheet 3 were at positions 3 and 4 respectively. A low-e coating was at position 2 ​​​​​The properties of the double glazing with coating were measured according to EN 410. The results are shown in the table. As stated in 5.

[0110] [Table 5]

[0111] In Table 5, the selectivity value is equal to the ratio of the light transmittance to the G value of the double glazing unit. Furthermore, each value is calculated using EN410, which is incorporated herein by reference.

[0112] When the viewing angles are 0° and 60°, the DGU prepared by coating according to Comparative Example 4 The difference in external reflections with respect to a* and b* is Δa* = 2.2 and Δb* = 2.5. This was found. Figure 5 shows a graph of the change in a* relative to the field of view in Example 4.

[0113] Furthermore, regarding the DGU prepared with the coating in Example 4, a color change of 3% occurred. The case is when Δa* = 2.9 and Δb* = 2.3. That is, according to the present invention The values ​​of Δa* and Δb* of the DGU prepared using the coating of Example 4 are within the acceptable limits. It is within the range of boundary 5, preferably within the range of limit 4, and even more preferably within limit It is within the range of 3.

[0114] (Summary of results) Therefore, from the above results, the coated glass sheet produced according to the present invention ( In other words, Examples 1 and 4) have good thick fibers with high selectivity 2.18 and 2.17. It can be seen that it provides sunlight control performance. Also, both Example 1 and Example 4 are facades This indicates that when placed in a certain position, the outer color changes slightly at different viewing angles. In this example as well, the color changes at different viewing angles when placed in a dual glazing unit Preferably, the values ​​of Δa* and Δb* are less than 3.0.

[0115] Regarding the manufacture of double glazing units (DGUs), the thickness of the coating layer changes. The ability to provide a DGU that shows little change in color as it progresses is important to the present invention. This is a key advantage. For both Examples 1 and 4, the coating stack sequence If the thickness variation of the fourth dielectric layer is 3%, then 3 is not applicable to both Δa* and Δb*. There was a change in Mitsuru.

[0116] In contrast, in Comparative Example 2, all silver layers were of the same thickness, and each induction necessary for the present invention was not present. The relationship between the optical thickness of the electrolytic layer is not satisfied, the selectivity is 2.07, and it is formed in DGU. Color shift of coated substrates at different viewing angles (0°-60°) when applied. In b*, it exceeds 5, and in reality, Δb* = 9.4. 3% of the second dielectric layer in Example 2 The color change due to the change in thickness also exceeds 5, with Δa* = 6.2 and Δb* = 8.0 respectively. ru.

[0117] In Comparative Example 3, the relationship for the optical thickness required for the dielectric layer according to the present invention is also not satisfied. Instead, the thickness of the optical layer of the dielectric layer in Example 3 increases as it moves away from the glass substrate. Instead, it decreases. Furthermore, the selectivity is 2.13, and it is coated according to Example 3. The color shift of the DGU, which is made of glass, at various viewing angles (0° to 60°) is In a*, the value exceeds 5, and in reality, Δa* = 12.1. Finally, the fourth induction of a* in Example 3 The color change recorded for a 3% thickness change in the electrolytic layer also exceeded 5, with a value of Δa* = 10.6. ru.

Claims

1. A double glazing unit incorporating a transparent substrate having a multilayer coating stack, wherein the coating stack is (i) n functional metal layers, m and (ii) comprising n plus 1 (n+1) dielectric layers, d, wherein the dielectric layers are arranged before and after each functional metal layer, Here, n is the total number of functional metal layers in the stack counted from the substrate, and is 3 or more. Here, each dielectric layer comprises one or more layers, The thickness Gm of the geometric layer of each functional metal layer in the multilayer coating stack is greater than the thickness of the geometric layer of each functional metal layer that appears before it in the multilayer coating stack, i.e., Gm ｉ＋１ >Gm ｉ And, Here, i is the position of the functional metal layer in the multilayer coating stack counted from the substrate, where, For each dielectric layer d located before and after each functional metal layer m, the thickness of the optical layer (opl) of each dielectric layer is considered to be... ｎ ) is the thickness of the optical layer of the dielectric layer placed before it in the coating stack (opl ｎ－１ ) and above, however, The thickness of the optical layer in the first dielectric layer of the coating stack (opl １ Twice the thickness of the optical layer of the second dielectric layer of the coating stack (opl ２ ) is smaller than (2x 0 pl １ ) <opl ２ And, The thickness (opl ｎ＋１ ) of the optical layer of the last dielectric layer of the coating stack is greater than twice the thickness (opl ｎ ) of the optical layer of the penultimate dielectric layer, that is, (opl ｎ ) < (opl ｎ＋１ ) x 2, and The angular dependence of external reflections of a* and b* from 0° to 60° includes 5 or less, more preferably 4.0 or less, and most preferably 3.0 or less. The color shift with a 3% thickness change includes 5 or less, more preferably 4.0 or less, and most preferably 3.0 or less. The aforementioned multilayer coating stack is First dielectric layer, d １ and, First functional metal layer m １ and, Second dielectric layer, d ２ and, Second functional metal layer m ２ and, Third dielectric layer, d ３ and, Third functional metal layer m ３ and, The fourth dielectric layer, d ４ and, Equipped with, The second or third dielectric layer d ２ or d ３ At least one of the transparent substrates is (i) A layer based on zinc (Zn) oxide and (ii) Layers based on oxides of zinc (Zn) and tin (Sn), It is equipped with the following in order, The fourth dielectric layer d ４ From the transparent substrate, (i) A layer based on zinc (Zn) oxide and (ii) Layers based on oxides of zinc (Zn) and tin (Sn), It is equipped with the following in order: A double glazing unit incorporating a transparent substrate equipped with the aforementioned multilayer coating stack.

2. The double glazing unit according to claim 1, wherein the functional metal layer comprises silver.

3. The double glazing unit according to claim 1 or 2, wherein the number n of functional metal layers in the multilayer coating stack includes 3 to 6.

4. The double glazing unit according to any one of claims 1 to 3, wherein the number of functional metal layers in the multilayer coating stack is 4.

5. Each dielectric layer consists of TiOx and SnO ２ , ZnO, ZAO, ZnO:Al, ZrOx, TiOx, Nb ２ O ５ Ta ２ O ５ In ２ O ３ Al ２ O ３ SiO ２ A double glazing unit according to any one of claims 1 to 4, comprising one or more layers of material selected from alloys or mixtures thereof, including ZnSnOx, InSnOx, and / or silicon (oxy)nitrides and / or aluminum (oxy)nitrides and / or alloys thereof.

6. The aforementioned multilayer coating stack is First dielectric layer, d １ and, First functional metal layer m １ and, Second dielectric layer, d ２ and, Second functional metal layer m ２ and, Third dielectric layer, d ３ and, Third functional metal layer m ３ and, The fourth dielectric layer, d ４ and, Fourth functional metal layer m ４ and, Fifth dielectric layer, d ５ and, A double glazing unit according to any one of claims 1 to 5, comprising:

7. The double glazing unit according to any one of claims 1 to 6, wherein each functional metal layer has a thickness of 5 to 25 nm.

8. The double glazing unit according to claim 6 or 7, wherein the first dielectric layer d1 comprises, in order from the transparent substrate, a layer based on titanium (Ti) oxide and / or a layer based on zinc (Zn) oxide.

9. The second, third, fourth, and fifth dielectric layers d ２ d ３ d ４ and d ５ Each of these is made from the transparent substrate, (i) A layer based on zinc (Zn) oxide and (ii) Zinc (Zn) and tin (Sn) oxides, and / or layers based on tin (Sn) oxide, A double glazing unit according to claim 6, 7, or 8, comprising the following in order.

10. Third dielectric layer d ３ The double glazing unit according to claim 9, further comprising a layer based on titanium (Ti) oxide.

11. Fifth dielectric layer d ５ The double glazing unit according to any one of claims 6 to 10, further comprising a layer based on zirconium (Zr) oxide.

12. The first dielectric layer d １ A double glazing unit according to any one of claims 6 to 11, wherein the thickness of the optical layer is in the range of 30 to 70 nm.

13. The second dielectric layer d ２ The double glazing unit according to any one of claims 6 to 12, wherein the thickness of the optical layer is in the range of 60 to 180 nm.

14. The third dielectric layer d ３ The double glazing unit according to any one of claims 6 to 13, wherein the thickness of the optical layer is in the range of 70 to 200 nm.

15. The fourth dielectric layer d ４ The double glazing unit according to any one of claims 6 to 14, wherein the thickness of the optical layer is in the range of 80 to 220 nm.

16. Fifth dielectric layer d ５ The double glazing unit according to any one of claims 6 to 15, wherein the thickness of the optical layer is in the range of 45 to 120.

17. The double glazing unit according to any one of claims 6 to 16, wherein the coating stack further comprises one or more layers based on NiCr.

18. The double glazing unit according to claim 17, wherein the NiCr-based layer or each NiCr-based layer is in direct contact with one or more silver functional layers.

19. A double glazing unit according to any one of claims 1 to 18, further comprising a selectivity of 1.9 or higher, more preferably 2.0 or higher, and most preferably 2.1 or higher.

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