Electrically conductive low-emissivity laminate

Abstract

The present invention relates to an electrically conductive low-emissivity laminate comprising a substrate; a high-refractive-index layer; a first coating film unit; a second coating film unit; and a third coating film unit, wherein the first coating film unit and the third coating film unit each independently comprise at least one first cross-layer set and at least one multilayer coating film set, the second coating film unit comprises at least one second cross-layer set and at least one multilayer coating film set, the first cross-layer set and the second cross-layer set each independently comprise at least one layer of a Si-containing transparent ceramic layer and a Zn-containing transparent ceramic layer, and the multilayer coating film set comprises a Zn-containing crystal nucleation layer, a functional conductive metal layer, and a functional conductive metal protective layer.

Description

Technology Field

[0001] The present invention relates to a low-emissivity laminate having electrical conductivity, and specifically to a low-emissivity glass having electrical conductivity that is heat-treatable or bendable. Background Technology

[0002] Low-emissivity glass is used to block external heat from moving into closed interiors, such as buildings and automobiles, due to its low emissivity. One method to achieve low radiation characteristics while maintaining visibility is to deposit a coating layer that transmits visible light and a coating layer that reflects solar rays on a transparent substrate that is visible in the visible light range (380–780 nm), such as glass.

[0003] Generally, due to its brittleness, glass tends to break easily despite its hardness. This brittleness can be compensated for by strengthening it through heat treatment. Since low-emissivity glass is manufactured by forming a coating layer on the glass, it also retains the characteristic of breaking from external impact. However, because the strength can be increased and the glass can be used after being strengthened by heat treatment at high temperatures, low-emissivity glass that remains usable even after heat treatment is very important.

[0004] The conductive metal layer used in low-emissivity glass generally utilizes metals with high electrical conductivity, such as Ag, Au, and Cu. However, these metals undergo degradation, such as crystallization, oxidation, and aggregation, at high heat treatment temperatures—typically above 600°C—which leads to defects and a loss of performance. In addition to high heat treatment temperatures, bending also causes degradation of the conductive metal layer, including crystallization, oxidation, and aggregation. To overcome these problems and maintain performance, a metal protective layer and various transparent ceramic layers are used together.

[0005] However, since the use of various metal, protective, and ceramic layers may result in undesirable properties such as transmittance, sheet resistance, color, and other characteristics, it is necessary to select materials, modify their arrangement, and establish process conditions to resolve these issues.

[0006] Therefore, there is a need to develop a low-emissivity laminate that can maintain its performance without the metal layer degrading even at high heat treatment temperatures. The problem to be solved

[0007] The problem that the present invention aims to solve is to provide a low-emissivity laminate that is electrically conductive and capable of heat treatment or bending, wherein there is no degradation of the conductive metal layer during heat treatment and bending, it exhibits high transmittance, and provides a low-emissivity laminate that performs heating and reflective functions by electricity. means of solving the problem

[0008] To solve the above problem, the present invention provides an electrically conductive low-emissivity laminate comprising a substrate; a high-refractive-index layer; a first coating film unit; a second coating film unit; and a third coating film unit, wherein the first coating film unit and the third coating film unit each independently comprise at least one first cross-layer set and at least one multilayer coating film set, the second coating film unit each comprises at least one second cross-layer set and at least one multilayer coating film set, the first cross-layer set and the second cross-layer set each independently comprise at least one layer of a Si-containing transparent ceramic layer and a Zn-containing transparent ceramic layer, and the multilayer coating film set comprises a Zn-containing crystal nucleation layer, a functional conductive metal layer, and a functional conductive metal protective layer. Effects of the invention

[0009] The present invention can provide an electrically conductive low-emissivity laminate that exhibits a heat-blocking effect due to low radiation and a heating function by electricity, and can also provide a reflection function for a head-up display (HUD) when necessary, while maintaining high transmittance and preventing degradation of the conductive metal layer even during heat treatment and bending. Specific details for implementing the invention

[0010] The present invention will be described in detail below.

[0012] The electrically conductive low-emissivity laminate according to the present invention comprises a substrate; a high-refractive-index layer; a first coating film unit; a second coating film unit; and a third coating film unit, which are sequentially laminated.

[0013] In an electrically conductive low-emissivity laminate according to the present invention, the first coating film unit and the third coating film unit each independently comprise at least one first cross-layer set and at least one multilayer coating film set, the second coating film unit each comprises at least one second cross-layer set and at least one multilayer coating film set, the first cross-layer set and the second cross-layer set each independently comprise at least one layer each of a Si-containing transparent ceramic layer and a Zn-containing transparent ceramic layer, and the multilayer coating film set comprises a Zn-containing crystal nucleation layer, a functional conductive metal layer, and a functional conductive metal protective layer.

[0015] An electrically conductive low-emissivity laminate according to one embodiment of the present invention may comprise: a substrate; a high-refractive-index layer disposed on the substrate; a first coating film unit disposed on the high-refractive-index layer; a second coating film unit disposed on the first coating film unit; and a third coating film unit disposed on the second coating film unit.

[0017] write

[0018] In one embodiment of the present invention, the substrate may be a glass substrate. As the glass substrate, ordinary glass such as soda-lime glass used for construction or automobiles may be used. Additionally, glass having a thickness of 1 mm to 12 mm may be freely used depending on the purpose of use, and for example, soda-lime glass with a thickness of 2.1 mm or 5 mm may be used.

[0020] High refractive index layer

[0021] In one embodiment of the present invention, the high refractive index layer may comprise a mixed metal nitride comprising Si and a metal. The high refractive index layer may serve to control the optical properties of an electrically conductive low-emissivity laminate. The high refractive index layer may have a refractive index of 1.9 to 2.5, specifically 2.0 to 2.4, and more specifically 2.0 to 2.3.

[0022] The mixed metal nitride containing Si and a metal may include, together with Si, one or more elements selected from Zr, Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni as the metal. Specifically, the mixed metal nitride containing Si and a metal may include Zr or Al as the metal, and more specifically, the mixed metal nitride containing Si and a metal may be SiZrN x (1 <x<2)일 수 있다.

[0024] 1st coating film unit

[0025] The first coating film unit comprises at least one of each of the first cross-layer set and the multilayer coating film set. Specifically, it may comprise one layer each of the first cross-layer set and the multilayer coating film set, and more specifically, it may comprise the first cross-layer set and the multilayer coating film set disposed on the first cross-layer set.

[0026] In one embodiment of the present invention, the first coating film unit may be disposed on the high refractive index layer.

[0028] 2nd coating film unit

[0029] The second coating film unit comprises at least one of each of the second cross-layer set and the multilayer coating film set, and specifically, may comprise a total of three or more of the second cross-layer set and the multilayer coating film set.

[0030] In one embodiment of the present invention, the second coating film unit may specifically include at least two of each of the second cross-layer set and the multilayer coating film set, and more specifically, may include at least three of the second cross-layer set and at least two of the multilayer coating film set.

[0031] In one embodiment of the present invention, when the second coating film unit includes at least two of each of the second cross-layer set and the multilayer coating film set, the second cross-layer set and the multilayer coating film set may be stacked alternately.

[0032] In one embodiment of the present invention, the second coating film unit comprises at least three sets of second cross-layers and at least two sets of multilayer coating films, and the second cross-layer sets and the multilayer coating film sets may be stacked alternately with each other. Specifically, the second coating film unit may comprise, for example, the second cross-layer set; a multilayer coating film set disposed on the second cross-layer set; a second cross-layer set disposed on the multilayer coating film set; the multilayer coating film set disposed on the second cross-layer set; and the second cross-layer set disposed on the multilayer coating film set.

[0033] When the second coating film unit includes three or more second cross-layer sets, the second cross-layer set, which is a transparent dielectric film, is alternately repeated with the multilayer coating film set, thereby preventing defects in the electrically conductive low-emissivity laminate from occurring even when the electrically conductive low-emissivity laminate is bent.

[0034] In one embodiment of the present invention, the multilayer coating film set may be interposed between a pair of second cross-layer sets facing each other. The number of the multilayer coating film sets included in the second coating film unit may be 'number of second cross-layer sets - 1', and the second cross-layer sets may be located at the bottom and top of the second coating film unit.

[0036] 3rd coating film unit

[0037] The above third coating film unit comprises at least one of each of the first cross-layer set and the multilayer coating film set, specifically, may comprise one layer each of the first cross-layer set and the multilayer coating film set, and more specifically, may comprise the multilayer coating film set and the first cross-layer set disposed on the multilayer coating film set.

[0038] In one embodiment of the present invention, the third coating film unit may be disposed on the second coating film unit.

[0040] (Cross-layer set)

[0041] The first cross-layer set and the second cross-layer set each independently comprise at least one layer of a Si-containing transparent ceramic layer and a Zn-containing transparent ceramic layer, respectively.

[0042] In one embodiment of the present invention, the first cross-layer set, which is independently included in the first coating film unit and the third coating film unit, may each have a Si-containing transparent ceramic layer and a Zn-containing transparent ceramic layer laminated thereon. Specifically, the first cross-layer set may have the Zn-containing transparent ceramic layer disposed on the Si-containing transparent ceramic layer, or the Si-containing transparent ceramic layer disposed on the Zn-containing transparent ceramic layer.

[0043] The thickness of the first cross-layer set may be 12 nm to 36 nm, specifically 15 nm to 33 nm, and more specifically 18 nm to 30 nm. At this time, the thickness ratio of the Si-containing transparent ceramic layer to the Zn-containing transparent ceramic layer of the first cross-layer set may be formed in a ratio of 1:0.2 to 1:2, specifically 1:0.7 to 1:1.5.

[0044] In one embodiment of the present invention, the first cross-layer set included in the first coating film unit and the first cross-layer set included in the third coating film unit may be positioned symmetrically with respect to the second coating film unit, and the Si-containing transparent ceramic layers and the Zn-containing transparent ceramic layers included in each may be positioned symmetrically with respect to each other.

[0045] For example, the first cross-layer set included in the first coating film unit may be located at the bottom of the first coating film unit, and specifically, may be located at the bottom of the first coating film unit with the Zn-containing transparent ceramic layer disposed on the Si-containing transparent ceramic layer.

[0046] For example, the first cross-layer set included in the third coating film unit may be located at the uppermost part of the third coating film unit, and may be located at the uppermost part of the third coating film unit with the Si-containing transparent ceramic layer disposed on the Zn-containing transparent ceramic layer.

[0047] The second cross-layer set above comprises at least one layer each of the Zn-containing transparent ceramic layer and the Si-containing transparent ceramic layer, specifically comprising at least two layers of the Zn-containing transparent ceramic layer and at least one layer of the Si-containing transparent ceramic layer, and more specifically comprising at least three layers of Zn-containing transparent ceramic layers and at least two layers of Si-containing transparent ceramic layers.

[0048] The thickness of the second cross-layer set may be 30 nm to 80 nm, specifically 35 nm to 70 nm, and more specifically 40 nm to 65 nm. At this time, the thickness ratio of the Si-containing transparent ceramic layer to the Zn-containing transparent ceramic layer of the second cross-layer set may be formed in a ratio of 1:2 to 1:5, specifically 1:2 to 1:4.

[0049] In one embodiment of the present invention, when the second cross-layer set includes at least two layers each of the Zn-containing transparent ceramic layer and the Si-containing transparent ceramic layer, the Zn-containing transparent ceramic layer and the Si-containing transparent ceramic layer may be stacked alternately.

[0050] In one embodiment of the present invention, the second cross-layer set may comprise at least three layers of Zn-containing transparent ceramic layers and at least two layers of Si-containing transparent ceramic layers, and the Zn-containing transparent ceramic layers and the Si-containing transparent ceramic layers may be stacked alternately with each other. Specifically, the second cross-layer set may comprise, for example, the Zn-containing transparent ceramic layer; the Si-containing transparent ceramic layer disposed on the Zn-containing transparent ceramic layer; the Zn-containing transparent ceramic layer disposed on the Si-containing transparent ceramic layer; the Si-containing transparent ceramic layer disposed on the Zn-containing transparent ceramic layer; and the Zn-containing transparent ceramic layer disposed on the Si-containing transparent ceramic layer.

[0051] In one embodiment of the present invention, the Si-containing transparent ceramic layer may be interposed between a pair of Zn-containing transparent ceramic layers facing each other. The number of Si-containing transparent ceramic layers included in the second set of intersecting layers may be "number of Zn-containing transparent ceramic layers minus 1," and the Zn-containing transparent ceramic layers may be located at the bottom and top of the second set of intersecting layers.

[0052] The first and second cross-layer sets are formed such that the Zn-containing transparent ceramic layer and the Si-containing transparent ceramic layer are intersected or repeated, and can serve to block oxygen or other unnecessary ions from being transferred or diffusing into the surroundings, i.e., the multilayer coating film set, during heat treatment such as strengthening or bending.

[0053] The above first cross-layer set and second cross-layer set include the Zn-containing transparent ceramic layer and the Si-containing transparent ceramic layer that intersect or repeat with each other, thereby preventing defects from occurring during bending of the electrically conductive low-emissivity laminate and serving to control the optical properties of the electrically conductive low-emissivity laminate.

[0054] The above Si-containing transparent ceramic layer may include silicon nitride, specifically SiN x It may include (x≤1.5).

[0055] The above Zn-containing transparent ceramic layer may include ZnSn-based composite metal oxides, specifically ZnSnO y It may include (1≤y≤2, Zn:Sn=52:48).

[0056] In one embodiment of the present invention, the Zn-containing transparent ceramic layer can serve to protect the functional conductive metal layer together with the facing Zn-containing crystal nucleation layer, help the crystallization of the functional conductive metal layer to increase conductivity, and enable the functional conductive metal layer to maintain a stable state during heat treatment. A detailed description of the Zn-containing crystal nucleation layer will be provided later.

[0058] (Multilayer coating film set)

[0059] The above multilayer coating film set comprises a Zn-containing crystal nucleation layer, a functional conductive metal layer, and a functional conductive metal protective layer. Specifically, the above multilayer coating film set may have a Zn-containing crystal nucleation layer; a functional conductive metal layer; a functional conductive metal protective layer; and a Zn-containing crystal nucleation layer sequentially stacked.

[0060] The above multilayer coating film set can be located between the first cross-layer set and the second cross-layer set, and between the second cross-layer set and the second cross-layer set, respectively.

[0061] The functional conductive metal layer described above is capable of exhibiting high electrical conductivity through the free electrons of the included metal and exhibits a relatively high reflectivity in the solar heat ray region of sunlight. By selectively reflecting solar radiation, it provides high shielding performance and simultaneously achieves low emissivity, thereby serving to provide a low thermal transmittance (U-value). The functional conductive metal layer may be composed of a material selected from Ag, Au, Cu, and combinations thereof, and specifically, may be composed of Ag (silver).

[0062] The thickness of the functional conductive metal layer included in the electrically conductive low-emissivity laminate may be the same or different from each other, specifically, different from each other. The thickness of the functional conductive metal layer may each independently be 6 nm to 25 nm, specifically 10 nm to 22 nm. If the thickness of the functional conductive metal layer is excessively thin, there is a concern that the formation of the conductive metal layer will not be properly carried out, resulting in insufficient electrical conductivity and low-emissivity performance; if the thickness is excessively thick, the transmittance may decrease, the durability of the electrically conductive low-emissivity laminate may decrease, and the defect rate may increase.

[0063] The functional conductive metal protective layer can be disposed on the functional conductive metal layer and serve to protect the functional conductive metal layer during coating, processing, and heat treatment. Specifically, the functional conductive metal protective layer can prevent oxidation caused by oxygen diffusion during coating and heat treatment, and prevent damage to the metal layer caused by friction from brushes, powders, and other contact materials during processing. In addition, when a glass substrate is applied as the substrate, the functional conductive metal protective layer can serve as a barrier to hinder the movement of Na ions and O2 diffusing from the glass during heat treatments such as strengthening and bending, and can assist in the fusion of the functional conductive metal so that the functional conductive metal layer can behave stably even under high heat treatment conditions. Finally, it can help maintain low-emission performance by absorbing O2 penetrating the functional conductive metal layer.

[0064] The above functional conductive metal protective layer is Ni, Cr, Ni-Cr alloy, and TiO z It may include one or more selected from the group consisting of (1≤z≤2), specifically Ni-Cr alloy or TiO z It may be composed of (1≤z≤2). In the case of the above Ni-Cr alloy, it may be an alloy of 75 wt% to 85 wt% Ni and 15 wt% to 25 wt% Cr.

[0065] In one embodiment of the present invention, the thickness of the functional conductive metal protective layer included in the electrically conductive low-emissivity laminate may be independently 0.1 nm to 3 nm, specifically 0.2 nm to 2.5 nm. Additionally, if the functional conductive metal protective layer comprises one or more selected from the group consisting of Ni, Cr, and Ni-Cr alloys, the thickness of the functional conductive metal protective layer may be independently 0.1 nm to 1.0 nm, specifically 0.2 nm to 0.5 nm, and the functional conductive metal protective layer may be TiO z When (1≤z≤2) is included, the thickness of the functional conductive metal protective layer may be independently 1.2 nm to 3.0 nm, and specifically 2.0 nm to 2.5 nm. If the thickness of the functional conductive metal protective layer is excessively thin, the blurring of the second coating film unit including it may increase after the heat treatment and bending process, and if the thickness of the functional conductive metal protective layer is excessively thick, the transmittance may decrease or the blurring of the second coating film unit may likewise increase after the heat treatment and bending process.

[0066] The above Zn-containing crystal nucleation layer is a transparent ceramic layer that is disposed below the functional conductive metal layer, that is, on the other side of the surface on which the functional conductive metal protective layer is disposed on the functional conductive metal layer, and can serve to protect the functional conductive metal layer. In addition, the above Zn-containing crystal nucleation layer helps the crystallization of the functional conductive metal layer to increase conductivity and can enable the functional conductive metal layer to maintain a stable state during heat treatment.

[0067] As described above, the Zn-containing crystal nucleation layer can serve to protect the functional conductive metal layer together with the facing Zn-containing transparent ceramic layer, to assist in the crystallization of the functional conductive metal layer to increase conductivity, and to maintain the functional conductive metal layer in a stable state during heat treatment. The Zn-containing crystal nucleation layer may be disposed on the Zn-containing transparent ceramic layer, or the Zn-containing transparent ceramic layer may be disposed on the Zn-containing crystal nucleation layer.

[0068] The above Zn-containing crystal nucleation layer may include zinc oxide, specifically ZnO y' It can be composed of (0.5≤y'≤2). In one embodiment of the present invention, the thickness of the Zn-containing crystal nucleation layer included in the electrically conductive low-emissivity laminate may be independently 3 nm to 12 nm, and specifically 3 nm to 7 nm. If the thickness of the Zn-containing crystal nucleation layer is thinner than the above range, the crystallization of the functional conductive metal layer may not be improved well, and if the thickness of the Zn-containing crystal nucleation layer is thicker than the above range, the transmittance may be lowered.

[0069] In one embodiment of the present invention, the multilayer coating film set may be sequentially laminated with a Zn-containing crystal nucleation layer; a functional conductive metal layer; a functional conductive metal protective layer; and a Zn-containing crystal nucleation layer. The Zn-containing crystal nucleation layer is ZnO y' (0.5≤y'≤2) is included, the functional conductive metal layer includes Ag, and the functional conductive metal protective layer includes NiCr and TiO z It may include one or more types selected from a group consisting of (1≤z≤2).

[0071] In one embodiment of the present invention, the electrically conductive low-emissivity laminate may additionally include an overcoat layer as a top coating layer. Specifically, the overcoat layer may include one or more selected from the group consisting of TiO2 and C, and more specifically may include TiO2 and C.

[0072] In one embodiment of the present invention, the overcoat layer may be at least one layer, specifically two layers, and the two overcoat layers may include a first overcoat layer comprising TiO2 and a second overcoat layer comprising C. The overcoat layer may include a first overcoat layer and a second overcoat layer disposed on the first overcoat layer.

[0073] In one embodiment of the present invention, the total thickness of the overcoat layer may be 1 nm to 10 nm, and specifically 2 nm to 8 nm. If the thickness of the overcoat layer is excessively thin, durability may be reduced, and if the thickness is excessively thick, it may cause a decrease in transmittance or cause blurring.

[0075] An electrically conductive low-emissivity laminate according to one embodiment of the present invention may have any one of the following multilayer structures:

[0076] Substrate / high refractive index layer / first coating film unit / second coating film unit / third coating film unit;

[0077] Substrate / high refractive index layer / first coating film unit / second coating film unit / third coating film unit / overcoat layer;

[0078] Specifically, substrate / high refractive index layer / first cross-layer set / multilayer coating film set / second cross-layer set / multilayer coating film set / second cross-layer set / multilayer coating film set / second cross-layer set / multilayer coating film set / first cross-layer set; or

[0079] Substrate / High refractive index layer / First cross-layer set / Multilayer coating film set / Second cross-layer set / Multilayer coating film set / Second cross-layer set / Multilayer coating film set / Second cross-layer set / Multilayer coating film set / First cross-layer set / Overcoat layer

[0081] The visible light transmittance of an electrically conductive low-emissivity laminate according to one embodiment of the present invention may be 60% or more, specifically 65% ​​or more, and more specifically 70% to 80% when measured according to the KS A 0066 standard using a Konica Minolta CM-3600A spectrophotometer.

[0082] In addition, an electrically conductive low-emissivity laminate according to one embodiment of the present invention may have a sheet resistance of 4.0 Ω / sq or less, specifically 0.5 Ω / sq to 1 Ω / sq, and more specifically 0.6 Ω / sq to 0.9 Ω / sq. The sheet resistance is a value measured by a silver (Ag) layer, which is a functional conductive metal layer, against solar rays, and is one of the evaluation properties that can assess the performance of an electrically conductive low-emissivity laminate or low-emissivity glass even after heat treatment or bending.

[0083] In addition, the electrically conductive low-emissivity laminate according to one embodiment of the present invention may have a reflectance of 5% to 25%, specifically 7% to 15%, and more specifically 8% to 12% after measuring the reflectance according to the KS L 2514 (ISO 13837) standard in the wavelength range of 380 to 780 nm.

[0084] An electrically conductive low-emissivity laminate according to one embodiment of the present invention may have an a* value of -10 to 5 and a b* value of 5 to -15 on the front side, and specifically, an a* value of -5 to 2 and a b* value of 0 to -15 on the front side.

[0085] An electrically conductive low-emissivity laminate according to one embodiment of the present invention may have an a* value of -5 to 5 and a b* value of 5 to -15 at the side view (observation angle 70°), specifically, an a* value of -3 to 3 and a b* value of 2 to -5 at the side view (observation angle 70°). In the case of the a*, a plus indicates red and a minus indicates green, and in the case of the b*, a plus indicates yellow and a minus indicates blue.

[0086] An electrically conductive low-emissivity laminate according to one embodiment of the present invention may have a TTS (Total Solar Transmission) of 20% to 60%, specifically 35% to 55%, when the transmittance / reflectance at wavelengths of 300 to 2500 nm is measured using a Konica Minolta CM-3600A spectrophotometer in accordance with ISO 13837.

[0088] Typically, the electrically conductive low-emissivity glass of the present invention can be manufactured using a vacuum sputtering method as a thin film forming method for laminating a high-refractive-index layer, a set of coating films and a set of cross-layers constituting each unit, and an overcoat layer that may optionally be included.

[0089] Although not limited thereto, according to one embodiment of the present invention, the electrically conductive low-emissivity glass of the present invention can be manufactured by the following procedure. First, a substrate is placed in a vacuum chamber and the vacuum level is 5×10 -7 to 9×10 -5A vacuum is formed by evacuating until the pressure reaches torr. Subsequently, argon (Ar), oxygen (O2), nitrogen (N2), etc., are injected into the vacuum chamber, and a direct or alternating current voltage is applied between two electrodes to cause a discharge. As a gas plasma is generated, gas ions collide with the cathode, on which a metal target to be deposited on the substrate is installed, causing atoms to be emitted from the metal target and deposited on the substrate. Depending on the type of coating film to be deposited, an appropriate gas is introduced, and the deposition rate of each coating film and the exposure time to the sputtering process are appropriately controlled to properly control the thickness of the coating film to be formed. At this time, there are no special limitations on the temperature of the substrate. The electrically conductive low-emissivity glass of the present invention can be manufactured by sequentially coating functional layers onto a glass substrate using a tubular magnetron sputtering coater. When coating a nitride film using argon and nitrogen, a SiZr metal target is used, and it is appropriate for the ratio of nitrogen in the mixed gas to be 40 volume% to 60 volume%. If the proportion of nitrogen is too high, the deposition rate of the film decreases, and if it is too low, the extinction coefficient increases, making it impossible to achieve high transmittance. When coating an oxide film using argon and oxygen, a ZnSn metal target is used, and the proportion of oxygen in the mixed gas is 40 volume% to 60 volume%. If the proportion of oxygen is too high, functional reflective metals (e.g., Ag) may oxidize during the coating process, and if the proportion of oxygen is too low, the coating may result in a metal film rather than a partial oxide film.

[0091] An electrically conductive low-emissivity laminate according to one embodiment of the present invention may be an electrically conductive low-emissivity glass, for example, an electrically conductive low-emissivity glass for construction or automobiles.

[0093] The present invention will be explained in more detail below through examples and comparative examples. However, the scope of the present invention is not limited to these examples.

[0095] [Examples and Comparative Examples]

[0096] Electrically conductive low-emissivity laminates were each manufactured by forming a multilayer coating film having the composition and thickness shown in Tables 1 to 4 below as Examples and Comparative Examples 1 to 3, respectively, on a transparent glass substrate with a thickness of 2.1 mm using a magnetron sputter coating machine.

[0097] SiZrN x' (x'=1.3) layer and SiN x (x=1.3) layer was coated under a nitrogen / argon atmosphere (nitrogen ratio: 45 to 60 vol%), and the ZnSnO (Zn:Sn=52:48) layer and ZnO layer were coated under an oxygen / argon atmosphere (oxygen ratio: 40 to 60 vol%) using a metal target. The Ag metal layer was coated under a 100% argon atmosphere. A NiCr alloy layer and TiO were used as barrier layers. z (1.6 <z<1.8) 층은 아르곤 100% 분위기 하에서 코팅되었다. 오버코트층으로서 TiO2층은 TiO z' (z'=1.9) The ceramic target was coated in an oxygen / argon mixture with an oxygen ratio of 5 to 10 volume%, and the C layer was coated in an argon atmosphere of 100 volume% using a carbon target.

[0098] Example 1 floor Thickness (nm) set Unit C Second overcoat layer 1.2 Overcoat layer TiO2 First overcoat layer 2.6 Without x (x=1.3) Si-containing transparent ceramic layer 11.2 3rd intersection layer set 3rd coating film unit ZnSnO(52:48) Zn-containing transparent ceramic layer 12.4 ZnO Zn-containing crystal nucleation layer 5.1 Multilayer coating film set TiO z (1.6 <z<1.8) Functional conductive metal protective layer 2.2 Ag functional conductive metal layer 11.8 ZnO Zn-containing crystal nucleation layer 5.5 ZnSnO(52:48) Zn-containing transparent ceramic layer 15.7 2nd cross layer set 2nd coating film unit Without x (x=1.3) Si-containing transparent ceramic layer 6.5 ZnSnO(52:48) Zn-containing transparent ceramic layer 14.5 Without x (x=1.3) Si-containing transparent ceramic layer 6.3 ZnSnO(52:48) Zn-containing transparent ceramic layer 15.2 ZnO Zn-containing crystal nucleation layer 5.1 Multilayer coating film set TiO z (1.6 <z<1.8) Functional conductive metal protective layer 2.2 Ag functional conductive metal layer 19.8 ZnO Zn-containing crystal nucleation layer 5.5 ZnSnO(52:48) Zn-containing transparent ceramic layer 14.1 2nd cross layer set Without x (x=1.3) Si-containing transparent ceramic layer 7.2 ZnSnO(52:48) Zn-containing transparent ceramic layer 12.9 Without x (x=1.3) Si-containing transparent ceramic layer 6.9 ZnSnO(52:48) Zn-containing transparent ceramic layer 13.0 ZnO Zn-containing crystal nucleation layer 5.1 Multilayer coating film set TiO z (1.6 <z<1.8) Functional conductive metal protective layer 2.2 Ag functional conductive metal layer 17.8 ZnO Zn-containing crystal nucleation layer 5.5 ZnSnO(52:48) Zn-containing transparent ceramic layer 14.3 2nd cross layer set Without x (x=1.3) Si-containing transparent ceramic layer 6.4 ZnSnO(52:48) Zn-containing transparent ceramic layer 11.0 Without x (x=1.3) Si-containing transparent ceramic layer 5.8 ZnSnO(52:48) Zn-containing transparent ceramic layer 14.1 ZnO Zn-containing crystal nucleation layer 5.1 Multilayer coating film set 1st coating film unit Ni-Cr Functional conductive metal protective layer 0.3 Ag functional conductive metal layer 16.4 ZnO Zn-containing crystal nucleation layer 5.5 ZnSnO(52:48) Zn-containing transparent ceramic layer 12.2 1st cross layer set Without x (x=1.3) Si-containing transparent ceramic layer 13.2 SiZrN x' (x'=1.3) High refractive index layer 11.6 - Glass write 2.1mm -

[0099] Comparative Example 1 floor Thickness (nm) C 1.5 TiO z (1.6 <z<1.8) 2 Without x (x=1.3) 27 ZnO 5.1 NiCr 0.3 Ag 11.8 ZnO 5.5 Without x (x=1.3) 62 ZnO 5.1 NiCr 0.3 Ag 19.8 ZnO 5.5 SiZrNx 22 Without x (x=1.3) 24 ZnO 5.1 NiCr 0.3 Ag 17.8 ZnO 5.5 Without x (x=1.3) 57 ZnO 5.1 NiCr 0.3 Ag 16.4 ZnO 5.5 SiZrN x' (x'=1.3) 37.4 Glass 2.1mm

[0100] Comparative Example 2 floor Thickness (nm) C 1.5 TiO2 2.6 ZnSnO(52:48) 13.2 Without x (x=1.3) 11.2 ZnO 5.1 TiO z (1.6 <z<1.8) 1.5 Ag 11.8 ZnO 5.5 Without x (x=1.3) 11.1 ZnSnO(52:48) 37.2 Without x (x=1.3) 11.1 ZnO 5.1 TiO z (1.6 <z<1.8) 1.5 Ag 19.8 ZnO 5.6 Without x (x=1.3) 11.1 ZnSnO(52:48) 33.3 Without x (x=1.3) 11.1 ZnO 5.1 NiCr 0.3 Ag 17.8 ZnO 5.5 Without x (x=1.3) 15 ZnSnO(52:48) 19 Without x (x=1.3) 15 ZnO 5.1 NiCr 0.3 Ag 16.4 ZnO 5.5 SiZrN x' (x'=1.3) 37.4 Glass 2.1mm

[0101] Comparative Example 3 floor Thickness (nm) C 1.5 ZnSnO(52:48) 8 Without x (x=1.3) 6.8 SiZrN x' (x'=1.3) 9.8 ZnO 5.1 TiO z (1.6 <z<1.8) 1.5 Ag 11.8 ZnO 5.6 ZnSnO(52:48) 20.2 SiZrN x' (x'=1.3) 10.6 Without x (x=1.3) 15.6 SiZrN x' (x'=1.3) 10.6 ZnO 5.1 TiO z (1.6 <z<1.8) 1.5 Ag 19.8 ZnO 5.6 ZnSnO(52:48) 16 SiZrN x' (x'=1.3) 10.6 Without x (x=1.3) 15.6 SiZrN x' (x'=1.3) 10.6 ZnO 5.1 TiO z (1.6 <z<1.8) 1.5 Ag 17.8 ZnO 5.6 ZnSnO(52:48) 19 SiZrN x' (x'=1.3) 11.6 Without x (x=1.3) 10.8 SiZrN x' (x'=1.3) 11.6 ZnO 5.1 NiCr 0.3 Ag 16.4 ZnO 5.5 ZnSnO(52:48) 12.2 Without x (x=1.3) 23.2 SiZrN x' (x'=1.3) 11.6 Glass 2.1mm

[0102] Experimental Example: Evaluation of Physical Properties

[0103] The electrically conductive laminates prepared in each of the above examples and comparative examples 1 to 3 were heat-treated under conditions in which the internal temperature was maintained at approximately 650°C or higher in a heat treatment furnace, heated for approximately 3 to 15 minutes depending on the glass thickness, and then slowly cooled.

[0104] In addition, separate samples prepared in the above Examples and Comparative Examples 1 to 3, respectively, were bent by the gravity of the glass in a forming tool inside a heat treatment furnace at a predetermined temperature and time.

[0105] These were each processed and evaluated into samples of 200×300 mm or larger.

[0107] 1. Appearance evaluation

[0108] For heat-treated samples and samples to which bending was applied, the occurrence of film cracking, haze, white dots, and appearance defects was checked.

[0109] (1) Film cracking defect: The surface condition of the sample was visually inspected from a distance of 50 cm to 100 cm. If no cracks occurred in the coating film, it was evaluated as good, and if defects occurred in the coating film, it was evaluated as poor.

[0110] (2) Haze defect: Observe the degree of haze on the surface of the overcoat layer visually and with a haze meter (BYK haze-gard plus Haze Meter Haze-gard) and the haze value It was evaluated as good if it was 1% or less, and poor if haze was visually confirmed or if the haze value exceeded 1%.

[0111] (3) Moisture resistance test: After leaving at 30°C and 80% humidity for more than 3 days, the number of shiny white defects with a diameter of 2.0 mm or more was checked. If no white defects were found, it was evaluated as good, and if white defects were observed, it was evaluated as poor.

[0112] (4) Appearance defects: The surface condition of the sample was visually inspected from a distance of 50 cm to 100 cm. If no defects were found in the coating film, the condition was evaluated as good, and if defects were visible to the naked eye in the coating film, it was evaluated as poor.

[0114] 2. Scratch Resistance Evaluation

[0115] Scratch resistance was evaluated by moving a nylon brush back and forth horizontally across the coated surface of the glass at least 10 times on the coated surface of the sample, and then measuring the number of scratches that occurred on the coated surface.

[0116] Specifically, it was evaluated as good if five or fewer scratches were generated, and as poor if more than five scratches occurred or if thick scratches of 1 mm or more in width occurred.

[0118] 3. Evaluation of Optical Properties After Bonding

[0119] After joining the heat-treated sample and the bent sample using a high-temperature, high-pressure autoclave method, optical properties were measured according to KS A 0066 and KS L 2514 (ISO 13837) standards, and color characteristics were measured according to CIE LAB 1976 a*, b* coordinates and scale (CIE 1976 a*b* diagram, D65 10-degree observer).

[0121] 4. Sheet Resistance Measurement

[0122] Surface resistance was measured using a non-contact surface resistance meter (manufactured by SURAGUS).

[0124] 5. TTS (Total Solar Transmission) Measurement

[0125] In accordance with ISO 13837, the transmittance / reflectance at wavelengths from 300 to 2500 nm was measured using a spectrophotometer (CM-3600A spectrophotometer, manufactured by Konica Minolta) and the TTS was calculated.

[0127] Plate thickness (2.1mm) Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Evaluation method After heat treatment Cracking defect Good Good error error Limit sample (visual) haze defect Good Good Good Good Limit sample (visual) and haze meter White Dot defect Good Good Good Good Limit sample (visual) exterior defects Good Good error error Limit sample (visual) After bending Cracking defect Good error error error Limit sample (visual) haze defect Good Good Good Good Limit sample (visual) and haze meter White Dot defect Good Good Good Good Limit sample (visual) exterior defects Good Good error error Limit sample (visual) Scratch Good Good Good error Limit sample (visual) Post-bonding optical properties Transmittance (%) 71.2 67.02 68.45 70.77 KS A 0066 reflectivity(%) 8.9 11.74 10.5 11.5 KS L 2514 Front a* -1.2 -9.43 -5.63 -4.76 CIE Lab Front b* -9.0 0.5 -0.11 -0.49 CIE Lab Side a* 1.2 2.29 0.27 0.29 CIE Lab Side b* -0.9 -0.36 0.31 0.27 CIE Lab Sheet resistance (electric furnace) 0.7 0.92 0.89 0.80 Surface resistance meter Tts(%) 40.0 ISO 13837

[0128] As shown in Table 3 above, the electrically conductive low-emissivity laminate of Example 1 did not exhibit defects due to film damage even during heat treatment and bending, and while exhibiting excellent scratch resistance, an appropriate level of reflectance for a head-up display (HUD), and high transmittance required for a windshield, it also showed a low level of color change. In addition, it was confirmed that it exhibited low sheet resistance without damage to the functional conductive metal layer, and that it could provide a heat-blocking effect due to excellent low-emissivity performance, as well as a heating function by electricity.

[0129] On the other hand, film cracking defects were observed in the electrically conductive low-emissivity laminates of Comparative Examples 1 to 3 after bending, and in the case of Comparative Examples 2 and 3, film cracking defects and appearance defects were additionally observed after heat treatment, and appearance defects after bending were observed together.

[0130] In the case of Comparative Example 1, no defects other than film cracking defects were observed after bending; however, it was confirmed that it was relatively inferior in terms of optical properties due to lower transmittance, higher reflectance, and larger color change values ​​compared to Example 1, and that its performance as a low-emissivity laminate was relatively inferior due to higher sheet resistance values ​​compared to Example 1. In the case of Comparative Examples 2 and 3, not only did film cracking defects and appearance defects occur after heat treatment and bending, respectively, but it was also confirmed that it was relatively inferior in terms of optical properties due to lower transmittance and higher reflectance values ​​compared to Example 1, and that its performance as a low-emissivity laminate was relatively inferior due to higher sheet resistance values ​​compared to Example 1. Among these, Comparative Example 3 was superior in optical properties and sheet resistance compared to Comparative Examples 1 and 2, but a problem of poor scratch resistance occurred, which did not occur in Comparative Examples 1 and 2.

[0131] Through these results, it can be confirmed that when the configuration of the present invention is satisfied, the electrically conductive low-emissivity laminate does not exhibit defects due to film damage even during heat treatment and bending, and can exhibit excellent scratch resistance, excellent optical properties, and an excellent thermal insulation effect as a low-emissivity laminate.

Claims

Claim 1 An electrically conductive low-emissivity laminate comprising a substrate; a high-refractive-index layer; a first coating film unit; a second coating film unit; and a third coating film unit, wherein the first coating film unit and the third coating film unit each independently comprise at least one first cross-layer set and at least one multilayer coating film set, and the second coating film unit comprises at least three second cross-layer sets and at least two multilayer coating film sets, and the second cross-layer sets and the multilayer coating film sets are stacked in an alternating manner, wherein the first cross-layer set comprises at least one layer each of a Si-containing transparent ceramic layer and a Zn-containing transparent ceramic layer, and the second cross-layer set comprises at least three layers of Zn-containing transparent ceramic layers and at least two layers of Si-containing transparent ceramic layers, and the multilayer coating film set comprises a Zn-containing crystal nucleation layer, a functional conductive metal layer, and a functional conductive metal protective layer. Claim 2 An electrically conductive low-emissivity laminate according to claim 1, wherein the substrate is a glass substrate, and the high-refractive-index layer comprises a mixed metal nitride comprising Si and a metal, and the mixed metal nitride comprising Si and a metal comprises one or more elements selected from Zr, Sn, Nb, Al, Sb, Mo, Cr, Ti and Ni as the metal. Claim 3 In claim 1, the first cross-layer set comprises a Si-containing transparent ceramic layer and a Zn-containing transparent ceramic layer laminated therein, and the Si-containing transparent ceramic layer is silicon nitride (SiN x , x≤1.5) is included, and the Zn-containing transparent ceramic layer comprises a ZnSn-based composite metal oxide (ZnSnO y An electrically conductive low-emissivity laminate comprising , 1≤y≤2). Claim 4 delete Claim 5 In claim 1, the second cross-layer set comprises at least two layers of Zn-containing transparent ceramic layers and at least one layer of Si-containing transparent ceramic layers stacked alternately with each other, wherein the Si-containing transparent ceramic layers comprise silicon nitride and the Zn-containing transparent ceramic layers comprise ZnSn-based composite metal oxide, an electrically conductive low-emissivity laminate. Claim 6 An electrically conductive low-emissivity laminate according to claim 1, wherein the multilayer coating film set comprises a Zn-containing crystal nucleation layer; a functional conductive metal layer; a functional conductive metal protective layer; and a Zn-containing crystal nucleation layer sequentially stacked. Claim 7 In claim 1, the Zn-containing crystal nucleation layer is ZnO y' (0.5≤y'≤2) is included, the functional conductive metal layer includes Ag, and the functional conductive metal protective layer includes NiCr and TiO z An electrically conductive low-emissivity laminate comprising one or more types selected from the group consisting of (1≤z≤2). Claim 8 The electrically conductive low-emissivity laminate according to claim 1, wherein the electrically conductive low-emissivity laminate further comprises an overcoat layer as an uppermost coating layer, and the overcoat layer comprises one or more selected from the group consisting of Ti, Si, Zr, Al, and C.

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