Low-emissivity heat-insulating glass which can be used in monolithic form and its production method and use

Abstract

The application relates to the technical field of heat-insulating glass, and particularly discloses low-radiation heat-insulating glass which can be used in a single piece, a preparation method and application thereof. The low-radiation heat-insulating glass comprises a glass body and a sandwich structure of an ITO film layer / Ag alloy layer / ITO film layer which are sequentially stacked. The application adopts AgNb alloy, limits the apparent thickness of the film layer to below 4 nm, and simultaneously adopts a process control means to form an island-shaped or interconnected network structure, so that the oxidation resistance of the film layer, the adhesion of the film layer, the weather resistance of the product and the processing adaptability can be effectively improved. Meanwhile, the application adopts an offline Low-E plating method to simultaneously realize the heat-insulating performance of ultralow radiation and the single-piece use performance, solves the problem that offline plating cannot be used in a single piece, and solves the problem that the online Low-E radiation is relatively high.

Description

Technical Field

[0001] This invention relates to the field of heat-insulating glass technology, specifically to a low-emissivity heat-insulating glass that can be used as a single piece, its preparation method, and its application. Background Technology

[0002] Currently, insulated glass is mainly divided into two categories: online Low-E glass and offline Low-E glass. Online Low-E glass products utilize CVD (Continuous Chemical Deposition) technology. While the glass substrate is at a high temperature, a reactive gas is introduced, depositing a film layer on the glass surface. Simultaneously, a chemical reaction occurs between the film and the substrate, resulting in a relatively strong film layer with certain low emissivity or thermal insulation properties. However, products produced using this method have relatively poor thermal insulation performance and emissivity. Generally, an emissivity of 0.25 or less is sufficient to classify it as online Low-E glass. Only glass with an emissivity less than 0.15 can be classified as offline Low-E coated glass. Offline Low-E coated glass is typically produced using large-scale vacuum magnetron sputtering equipment for PVD. The functional layer material usually contains Ag, Cu, or AgCu alloys. However, Low-E containing Ag readily reacts with moisture, sulfur dioxide, and hydrogen sulfide in the air, damaging the thermal insulation performance of the coating and causing oxidation and appearance defects. Therefore, offline Low-E products cannot be used as single panes and must be manufactured as hollow units to isolate moisture, sulfur dioxide, and hydrogen sulfide from the air. Although offline Low-E glass offers superior thermal insulation and lower emissivity compared to online Low-E glass, the need for hollow units significantly increases cost and weight, limiting its applications. If the high thermal insulation performance of offline-coated Low-E products could be utilized while simultaneously addressing the issue of single-pane usability, its application scenarios would be greatly expanded, and costs and weight reduced.

[0003] Existing offline Low-E glass has low emissivity and good thermal insulation performance, but it cannot be used as a single piece. It needs to be made into hollow units to isolate gases such as water vapor, sulfur dioxide and hydrogen sulfide in the air, which increases the thickness, weight and cost, thus limiting its application scenarios.

[0004] While existing online Low-E insulated glass can be used as a single pane, its high emissivity results in insufficient heat insulation and thermal insulation performance, leading to increased indoor air conditioning load. Furthermore, the variety of online Low-E products is limited, and their performance, optical properties, and thermal properties are not adjustable, restricting their market application scope and selectivity.

[0005] Therefore, it is necessary to provide a low-emissivity insulating glass that can be used as a single piece, its preparation method and application, to maintain a low emissivity in offline Low-E glass while achieving the single-piece use function of the product. Summary of the Invention

[0006] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a low-emissivity heat-insulating glass that can be used in single pieces, its preparation method and application, which maintains the low emissivity of offline Low-E glass while realizing the single-piece use function of the product.

[0007] The inventive concept of this invention is as follows: This invention involves preparing and repeatedly stacking an ITO film layer / Ag alloy layer / ITO film layer sandwich structure on a glass substrate. When the Ag alloy layer is an AgNb alloy, the AgNb alloy effectively improves the oxidation resistance of Ag. When oxygen enters the interior of the film layer, it is first captured by Nb atoms to form NbOx, which effectively prevents further oxidation of Ag by oxygen atoms, thus protecting the overall film layer from oxidation. The ITO surface forms a concave-convex structure, which, while forming embedded island-like or interconnected network AgNb alloys, effectively increases the embedding depth between film layers and enhances the bonding and adhesion between them. Furthermore, ITO material possesses inherent acid and alkali resistance and low emissivity, while the island-like or interconnected network Ag alloy layer further effectively reduces the emissivity of the film layer. This achieves the monolithic usability and low emissivity of the overall film layer, improves thermal insulation and heat preservation performance, increases the product's processability, oxidation resistance, and product adaptability, reduces costs, and expands the range of application scenarios.

[0008] A first aspect of the present invention provides a low-emissivity heat-insulating glass that can be used as a single piece.

[0009] Specifically, the low-emissivity heat-insulating glass includes a glass body and an ITO film layer / Ag alloy layer / ITO film layer sandwich structure formed by sequentially stacking layers.

[0010] Preferably, the thickness of the ITO (indium tin oxide) film is 25–73 nm.

[0011] Preferably, the total thickness of the ITO film is 125–180 nm.

[0012] To ensure an emissivity of no less than 0.15, the thickness of a single ITO film layer needs to be controlled to be no less than 25 nm, and the total thickness of the ITO film layer needs to be no less than 125 nm. Furthermore, the total thickness of the ITO film layer cannot exceed 180 nm. While a thicker ITO film layer can reduce emissivity, it affects production speed. Additionally, a thicker film layer results in a significant increase in reflectivity and a color that deviates from neutral tones, making it difficult to meet market demands.

[0013] Preferably, the Ag alloy layer is an AgNb alloy; the thickness of the Ag alloy layer is 1–4 nm.

[0014] Preferably, the surface roughness (Ra) of the ITO film is 0.1–2 nm. A surface roughness (Ra) of less than 2 nm promotes the formation of an uneven structure. AgNb is then deposited on this uneven structure, causing the AgNb alloy to form island-like or interconnected network structures on the surface of the ITO uneven structure.

[0015] Preferably, the ratio of Ag to Nb in the Ag alloy layer is 4 to 19:1.

[0016] More preferably, the Ag alloy layer is prepared by sputtering an alloy target with Ar gas or by co-sputtering with two targets.

[0017] More preferably, the two target materials are Ag and Nb.

[0018] Preferably, the low-emissivity insulating glass further includes a bottom dielectric layer; the bottom dielectric layer includes at least one of SiNx, SiOx, and SiNxOy. The bottom dielectric layer prevents alkali metal precipitation while regulating optical properties.

[0019] Preferably, the low-emissivity insulating glass further includes an outer dielectric layer; the outer dielectric layer includes at least one of SiNx, SiOx, SiNxOy, ZrOx, and TiOx. The outer dielectric layer adjusts the optical properties while protecting the inner film layer.

[0020] A second aspect of the present invention provides a method for preparing low-emissivity heat-insulating glass that can be used in single sheets.

[0021] Specifically, it includes the following steps:

[0022] (1) A base dielectric layer is deposited on the glass body;

[0023] (2) Deposit an ITO film layer on the underlying dielectric layer;

[0024] (3) An Ag alloy layer is deposited on the surface of the ITO film to form an island structure or an interconnected network structure;

[0025] (4) Deposit an ITO film layer on an island structure or a connected network structure to form a sandwich structure;

[0026] (5) Repeat steps (3) and (4) to stack the sandwich structure;

[0027] (6) A low-emissivity heat-insulating glass is obtained by depositing an outer dielectric layer on the outermost surface.

[0028] Preferably, in step (5), the number of times the layers are stacked is 0 to 3.

[0029] Preferably, in step (3), an Ag alloy layer is deposited on the surface of the ITO film to form an interconnected network structure.

[0030] The sandwich structure further reduces the emissivity of the overall composite membrane layer and improves its thermal insulation performance.

[0031] A third aspect of the present invention provides an application of a single-pane low-emissivity insulating glass in architectural glass, automotive glass, and refrigerator door glass.

[0032] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0033] (1) The present invention contains Ag alloy coated glass, which achieves single-piece performance, reduces costs, and expands application scenarios.

[0034] (2) The present invention significantly reduces the emissivity and surface resistivity of glass, which can effectively increase the thermal insulation performance; thereby reducing the indoor air conditioning load and is conducive to environmental protection and energy conservation.

[0035] (3) The present invention uses AgNb alloy and limits the apparent thickness of its film to less than 4nm. At the same time, process control methods are used to form an island-like or interconnected network structure, which can effectively improve the oxidation resistance, adhesion, weather resistance and processing adaptability of the film.

[0036] (4) The present invention guarantees an emissivity of less than 0.15, a total ITO thickness of not less than 125 nm, and a single-layer ITO thickness of not less than 25 nm. At the same time, in order to ensure low reflectivity and neutral color, the total ITO thickness does not exceed 180 nm.

[0037] (5) The present invention adopts an offline Low-E plating method, which simultaneously achieves thermal insulation performance with ultra-low emissivity and single-piece use performance, solving the problems that offline plating cannot be used as a single piece and that online Low-E emissivity is too high. Attached Figure Description

[0038] Figure 1 This is a schematic diagram of the sandwich structure of the ITO film layer / Ag alloy layer / ITO film layer of the present invention. Detailed Implementation

[0039] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.

[0040] Unless otherwise specified, the raw materials, reagents or devices used in the following examples are available from conventional commercial sources or can be obtained by existing known methods.

[0041] Example 1

[0042] A low-emissivity insulating glass that can be used in single sheets and its preparation method.

[0043] The low-emissivity insulating glass that can be used as a single piece includes a glass body and, in sequence, a SiOx bottom dielectric layer, an ITO film layer 1, an Ag alloy layer, an ITO film layer 2, and a SiNx outer dielectric layer. The Ag alloy layer is an AgNb alloy.

[0044] The glass body thickness is 6 nm; the SiOx bottom dielectric layer thickness is 25 nm; the ITO film layer 1 thickness is 72 nm; the Ag alloy layer thickness is 4 nm; the ITO film layer 2 thickness is 72 nm; and the SiNx outer dielectric layer thickness is 35 nm. The surface roughness Ra of all ITO films is 1.8 nm.

[0045] The preparation method includes the following steps:

[0046] (1) A SiOx substrate dielectric layer is deposited on the glass substrate;

[0047] (2) Deposit an ITO film layer 1 on the underlying dielectric layer;

[0048] (3) An Ag alloy layer is deposited on the surface of the ITO film layer 1, and an AgNb alloy interconnected network structure is formed;

[0049] (4) An ITO film 2 is deposited on the AgNb interconnected network structure to form a sandwich structure;

[0050] (5) A SiNx outer dielectric layer is deposited on the outermost surface to obtain low-emissivity heat-insulating glass.

[0051] Example 2

[0052] A low-emissivity insulating glass that can be used in single sheets and its preparation method.

[0053] Low-emissivity insulating glass that can be used as a single piece includes a glass body and, in order of appearance, a SiOx bottom dielectric layer, an ITO film layer 1, an Ag alloy layer 1, an ITO film layer 2, an Ag alloy layer 2, an ITO film layer 3, and a SiN layer. x O y Outer dielectric layer. The Ag alloy layer is an AgNb alloy.

[0054] The glass substrate thickness is 6 nm; the SiOx bottom dielectric layer thickness is 48.8 nm; the ITO film layer 1 thickness is 56.1 nm; the Ag alloy layer 1 thickness is 2 nm; the ITO film layer 2 thickness is 50.2 nm; the Ag alloy layer 2 thickness is 3 nm; the ITO film layer 3 thickness is 40.7 nm; SiN x O y The outer dielectric layer is 34 nm thick. The surface roughness Ra of all ITO films is 1.8 nm.

[0055] The preparation method includes the following steps:

[0056] (1) A SiOx substrate dielectric layer is deposited on the glass substrate;

[0057] (2) Deposit an ITO film layer 1 on the underlying dielectric layer;

[0058] (3) An Ag alloy layer 1 is deposited on the surface of the ITO film layer 1, and an AgNb alloy interconnected network structure is formed;

[0059] (4) An ITO film 2 is deposited on the AgNb interconnected network structure to form a sandwich structure;

[0060] (5) Repeat steps (3) and (4) to perform one stacking of the sandwich structure; that is, deposit Ag alloy layer 2 on the surface of ITO film layer 2 and form AgNb alloy interconnected network structure; deposit ITO film layer 3 on AgNb interconnected network structure to form sandwich structure.

[0061] (6) Deposit SiN on the outermost surface x O y The outer dielectric layer is used to make low-emissivity heat-insulating glass.

[0062] Example 3

[0063] A low-emissivity insulating glass that can be used in single sheets and its preparation method.

[0064] The low-emissivity insulating glass that can be used in a single piece includes a glass body and, in order of appearance, a SiOx bottom dielectric layer, an ITO film layer 1, an Ag alloy layer 1, an ITO film layer 2, an Ag alloy layer 2, an ITO film layer 3, and a SiNx outer dielectric layer. The Ag alloy layer is an AgNb alloy.

[0065] The glass substrate thickness is 6 nm; the SiOx bottom dielectric layer thickness is 40 nm; the ITO film layer 1 thickness is 67.2 nm; the Ag alloy layer 1 thickness is 2 nm; the ITO film layer 2 thickness is 61.3 nm; the Ag alloy layer 2 thickness is 3 nm; the ITO film layer 3 thickness is 51.5 nm; and the SiNx outer dielectric layer thickness is 37 nm. The surface roughness Ra of all ITO films is 1.5 nm.

[0066] The preparation method includes the following steps:

[0067] (1) A SiOx substrate dielectric layer is deposited on the glass substrate;

[0068] (2) Deposit an ITO film layer 1 on the underlying dielectric layer;

[0069] (3) An Ag alloy layer 1 is deposited on the surface of the ITO film layer 1, and an AgNb alloy interconnected network structure is formed;

[0070] (4) An ITO film 2 is deposited on the AgNb interconnected network structure to form a sandwich structure;

[0071] (5) Repeat steps (3) and (4) to perform one stacking of the sandwich structure; that is, deposit Ag alloy layer 2 on the surface of ITO film layer 2 and form AgNb alloy interconnected network structure; deposit ITO film layer 3 on AgNb interconnected network structure to form sandwich structure.

[0072] (6) A SiNx outer dielectric layer is deposited on the outermost surface to obtain low-emissivity heat-insulating glass.

[0073] Example 4

[0074] A low-emissivity insulating glass that can be used in single sheets and its preparation method.

[0075] The low-emissivity insulating glass that can be used as a single piece includes a glass body and, in order of appearance, a SiOx bottom dielectric layer, an ITO film layer 1, an Ag alloy layer 1, an ITO film layer 2, an Ag alloy layer 2, an ITO film layer 3, an Ag alloy layer 3, an ITO film layer 4, a SiOx outer dielectric layer, and a ZrOx outer dielectric layer. The Ag alloy layer is an AgNb alloy.

[0076] The glass substrate thickness is 6 nm; the SiOx bottom dielectric layer thickness is 62 nm; the ITO film layer 1 thickness is 51 nm; the Ag alloy layer 1 thickness is 2.5 nm; the ITO film layer 2 thickness is 48 nm; the Ag alloy layer 2 thickness is 3.5 nm; the ITO film layer 3 thickness is 25 nm; the Ag alloy layer 3 thickness is 4 nm; the ITO film layer 4 thickness is 40 nm; the SiOx outer dielectric layer thickness is 25 nm; and the ZrOx outer dielectric layer thickness is 4 nm. The surface roughness Ra of all ITO films is 1.5 nm.

[0077] The preparation method includes the following steps:

[0078] (1) A SiOx substrate dielectric layer is deposited on the glass substrate;

[0079] (2) Deposit an ITO film layer 1 on the underlying dielectric layer;

[0080] (3) An Ag alloy layer 1 is deposited on the surface of the ITO film layer 1, and an AgNb alloy interconnected network structure is formed;

[0081] (4) An ITO film 2 is deposited on the AgNb interconnected network structure to form a sandwich structure;

[0082] (5) Repeat steps (3) and (4) to perform two superpositions of the sandwich structure; that is, deposit Ag alloy layer 2 on the surface of ITO film layer 2 and form AgNb alloy interconnected network structure; deposit ITO film layer 3 on AgNb interconnected network structure to form sandwich structure; deposit Ag alloy layer 3 on the surface of ITO film layer 3 and form AgNb alloy interconnected network structure; deposit ITO film layer 4 on AgNb interconnected network structure to form sandwich structure;

[0083] (6) A SiOx outer dielectric layer is deposited on the outermost surface, and then a ZrOx outer dielectric layer is deposited on the SiOx outer dielectric layer to obtain low-emissivity heat-insulating glass.

[0084] Comparative Example 1

[0085] A low-emissivity insulating glass that can be used in single sheets and its preparation method.

[0086] The difference between Comparative Example 1 and Example 1 is that the thickness of the Ag alloy layer in Comparative Example 1 is 5 nm.

[0087] Comparative Example 2

[0088] A low-emissivity insulating glass that can be used in single sheets and its preparation method.

[0089] The difference between Comparative Example 2 and Example 1 is that the thickness of ITO film 1 in Comparative Example 2 is 92 nm; the thickness of ITO film 2 is 92 nm.

[0090] Comparative Example 3

[0091] A low-emissivity insulating glass that can be used in single sheets and its preparation method.

[0092] The difference between Comparative Example 3 and Example 1 is that there is no Ag alloy layer in Comparative Example 3.

[0093] Effect detection and analysis:

[0094] 1. Analysis of color data, transmittance, surface resistivity, and emissivity data.

[0095] Color data: measured using a spectrophotometer; transmittance: measured using a spectrophotometer; surface resistivity: measured using the Filmonitor optical inspection and analysis management system; emissivity: measured using a glass emissivity meter.

[0096] The color data, transmittance, sheet resistivity, and emissivity data of Examples 1-4 and Comparative Examples 1-2 are shown in Table 1. In Comparative Example 2, the total ITO thickness exceeds 180 nm. Although its sheet resistivity and emissivity are low, the film brightness is high, the color is poor, and the visible light transmittance is low. In contrast, Comparative Example 3, lacking the Ag alloy layer, shows a significant increase in both sheet resistivity and emissivity.

[0097] Table 1 Color data, transmittance, surface resistance and emissivity data of Examples 1-4 and Comparative Examples 1-2

[0098]

[0099]

[0100] 2. Acid and alkali resistance test analysis.

[0101] The acid and alkali resistance test was carried out in accordance with GB / T 18915.1-2013 "Coated glass - Part 1: Solar control coated glass", that is, the acid resistance test was to immerse the specimen in hydrochloric acid with a concentration of 1 mol / L at (23±2)°C for 24 hours; the alkali resistance test was to immerse the specimen in sodium hydroxide with a concentration of 1 mol / L at (23±2)°C for 24 hours. The absolute value of the difference in the average visible light transmittance before and after the test should not be greater than 4%, and there should be no obvious change in the film layer to be qualified. The acid and alkali resistance data of Examples 1-4 and Comparative Examples 1-2 are shown in Table 2. In Comparative Example 1, the Ag alloy layer was thicker, and the change value of the film layer transmittance in the acid resistance experiment was greater than 4%, which was unqualified.

[0102] Table 2 Acid and alkali resistance data of Examples 1-4 and Comparative Examples 1-2

[0103]

[0104] The preferred specific embodiments of the present invention have been described in detail above. It should be understood that those of ordinary skill in the art can make many modifications and variations based on the concept of the present invention without creative work. Therefore, any technical solutions obtained by those skilled in the art in the technical field of the present invention through logical analysis, reasoning or limited experiments based on the concept of the present invention on the basis of the prior art, such as any modifications, equivalent replacements, improvements, etc., should be within the protection scope determined by the claims.

Claims

1. A low-emissivity heat-insulating glass that can be used as a single piece, characterized in that, The low-emissivity heat-insulating glass comprises a glass body and an ITO film layer / Ag alloy layer / ITO film layer sandwich structure formed by sequentially stacking layers. The thickness of the ITO film is 25~73 nm. The total thickness of the ITO film is 125~180nm; The Ag alloy layer is an AgNb alloy; the thickness of the Ag alloy layer is 1~4 nm; The surface roughness of the ITO film is 0.1~2nm, which forms an uneven structure on the surface of the ITO film. The AgNb alloy forms an island-like or interconnected network structure on the uneven surface of the ITO film.

2. The low-emissivity heat-insulating glass according to claim 1, characterized in that, The low-emissivity heat-insulating glass further includes a bottom dielectric layer; the bottom dielectric layer includes at least one of SiNx, SiOx, and SiNxOy.

3. The low-emissivity heat-insulating glass according to claim 1, characterized in that, The low-emissivity heat-insulating glass further includes an outer dielectric layer; the outer dielectric layer includes at least one of SiNx, SiOx, SiNxOy, ZrOx, and TiOx.

4. The method for preparing low-emissivity heat-insulating glass according to any one of claims 1 to 3, characterized in that, Includes the following steps: (1) A base dielectric layer is deposited on the glass body; (2) Deposit an ITO film layer on the underlying dielectric layer; (3) An Ag alloy layer is deposited on the surface of the ITO film to form an island structure or an interconnected network structure; (4) Deposit an ITO film on an island-like structure or a connected network structure to form a sandwich structure; (5) Repeat steps (3) and (4) to stack the sandwich structure; (6) A low-emissivity heat-insulating glass is obtained by depositing an outer dielectric layer on the outermost surface.

5. The preparation method according to claim 4, characterized in that, In step (5), the number of times the layers are stacked is 0 to 3.

6. The application of the low-emissivity insulating glass according to any one of claims 1 to 3 in architectural glass, automotive glass, and refrigerator door glass.

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