A multi-silver layer low-emissivity coated glass containing a crystalline dielectric layer, a preparation method thereof, and uses thereof

Abstract

The present invention provides a multi-silver-layer low-emissivity coated glass containing a crystalline dielectric layer, and a preparation method and use thereof. The film layer structure of the coated glass includes, from the glass substrate outwards: a glass substrate, at least three continuously arranged composite low-emissivity functional layers, and a protective layer; a dielectric layer is provided on each of the inner and outer sides of the composite low-emissivity functional layer; the composite low-emissivity functional layer sequentially includes a first crystalline dielectric layer, a silver layer, and a second crystalline dielectric layer which are superposed along the direction from the glass substrate outwards. The coated glass of the present invention is prepared by a vacuum magnetron sputtering coating method, and the coated glass is used as an automotive front windshield laminated glass or a building energy-saving glass. Through testing, the obtained coated glass has a high transmittance and a low shading coefficient, and can be bent and tempered at the same time, which can meet the requirements of the automotive field and the construction industry for coated glass, and is more suitable for market demand.

Description

Technical Field

[0001] The present invention relates to the field of coated glass for buildings and automobiles, and relates to a multi-silver layer low-emissivity coated glass and its preparation method and use, and particularly relates to a multi-silver layer low-emissivity coated glass containing a crystalline dielectric layer and its preparation method and use. Background Art

[0002] Low-emissivity coated glass is a new generation of coated glass that can allow solar energy and visible light outdoors to pass through like ordinary glass, and can also reflect the secondary radiant heat of objects back like an infrared mirror. When used in any climate environment, it can achieve the functions of controlling light, saving energy and heat, controlling and regulating, and improving the environment. Traditional low-emissivity glass includes single-silver and double-silver coated glass. In order to obtain a lower shading coefficient and a good light-to-heat ratio, only by continuously increasing the thickness of the silver layer. However, the increase in the thickness of the silver layer means a decrease in the transmission of visible light and limited color selection, which cannot meet the needs of different customers. Therefore, more complex triple-silver or even quadruple-silver low-emissivity coated glass has emerged.

[0003] CN 110092594A discloses a triple-silver coated glass and its preparation method. The triple-silver coated glass sequentially includes a glass substrate layer, a first dielectric layer, a first silver layer, a second dielectric layer, a second silver layer, a third dielectric layer, a third silver layer, and a fourth dielectric layer from one side to the other side; the first dielectric layer, the second dielectric layer, the third dielectric layer, and the fourth dielectric layer are all multi-layer dielectric layers, and are respectively selected from at least two of Si3N4 layer, TiO x layer, SnO y layer, ZnO z layer, ZnSnO a+b layer, and AZO layer; where 0 < x ≤ 2, 0 < y ≤ 2, 0 < z ≤ 1, 0 < b ≤ 2, 0 < a ≤ 1.

[0004] CN 102514279A discloses a quadruple-silver low-emissivity coated glass and its manufacturing process. The quadruple-silver low-emissivity coated glass is provided with a coating on a glass substrate. The coating layers from the glass substrate outwards are: a first dielectric combination layer, a first silver layer, a first spacer layer dielectric combination layer, a second silver layer, a second spacer layer dielectric combination layer, a third silver layer, a third spacer layer dielectric combination layer, a fourth silver layer, and a second dielectric combination layer.

[0005] CN 102092959 A discloses a high-shading triple-silver low-emissivity coated glass containing a three-layer composite antireflection layer and its manufacturing process. The structural layers of the product from the glass substrate outwards are successively: glass / composite antireflection layer (1) + silver layer (1) + protective layer (1) + composite antireflection layer (2) + silver layer (2) + protective layer (2) + composite antireflection layer (3) + silver layer (3) + protective layer (3) + dielectric layer (1); the product adopts a vacuum magnetron sputtering coating process.

[0006] The above patent provides coated glass with different film layer structures, but there are limitations on the number of silver layers. As the number of silver layers increases, it is impossible to ensure the advantages of high transmittance and low shading coefficient of the coated glass. Therefore, it is necessary to further improve the coated glass in terms of performance. How to provide a coated glass that not only has multiple silver layers but also has the advantages of high transmittance and low shading coefficient has become an urgent problem to be solved. Summary of the Invention

[0007] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a multi-silver layer low-emissivity coated glass containing a crystalline medium, its preparation method and uses. The multi-silver layer low-emissivity coated glass containing a crystalline medium provided by the present invention has high transmittance and low shading coefficient, and can be bent and tempered at the same time, which can meet the requirements of the coated glass in the building and automotive fields and is more suitable for market demand.

[0008] To achieve this purpose, the present invention adopts the following technical solutions:

[0009] In the first aspect, the present invention provides a multi-silver layer low-emissivity coated glass containing a crystalline medium. The film layer structure of the multi-silver layer low-emissivity coated glass containing a crystalline medium from the glass substrate outwards includes: a glass substrate, at least 3 continuously arranged composite low-emissivity functional layers, and a protective layer;

[0010] One dielectric layer is arranged on each of the inner and outer sides of the composite low-emissivity functional layer;

[0011] The composite low-emissivity functional layer successively includes a first crystalline medium layer, a silver layer, and a second crystalline medium layer which are superposed from the glass substrate outwards.

[0012] The film layer structure of the multi-silver layer low-emissivity coated glass includes at least 3 continuously arranged composite low-emissivity functional layers and dielectric layers. For example, it can be 3 layers, 4 layers, 6 layers, 8 layers or 12 layers, but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0013] The statement in the present invention that "a dielectric layer is provided on each of the inner and outer sides of the composite low-emissivity functional layer" means that, in the direction outward from the glass substrate, a dielectric layer is provided on each of the inner and outer sides of each composite low-emissivity functional layer. Taking three continuously arranged composite low-emissivity functional layers as an example, the film layer structure is: glass substrate, dielectric layer, composite low-emissivity functional layer, dielectric layer, composite low-emissivity functional layer, dielectric layer, composite low-emissivity functional layer, dielectric layer, protective layer.

[0014] The film layer structure of the coated glass in the present invention includes at least three continuously arranged composite low-emissivity functional layers. Each composite low-emissivity functional layer includes a first crystalline dielectric layer, a silver layer, and a second crystalline dielectric layer, thus constituting a multi-silver-layer coated glass; the emissivity of the multi-silver-layer low-emissivity coated glass containing a crystalline dielectric layer provided by the present invention is ≤0.018.

[0015] The first crystalline dielectric layer and the second crystalline dielectric layer in the present invention have the advantages of high thermal stability, chemical and corrosion resistance, and salt spray resistance, and have excellent protection effects on the silver layer. At the same time, the first crystalline dielectric layer and the second crystalline dielectric layer can serve as good crystal beds for the metal silver layer, enabling the silver layer to grow well. The first crystalline dielectric layer and the second crystalline dielectric layer have a relatively high refractive index (n>2), which greatly improves the visible light transmittance and extends the service life of the coated glass.

[0016] Preferably, the material of the dielectric layer includes any one or a combination of at least two of Si3N4, TiO2, ZnSnO x , ZrO2, NbO y or TaO. Typical but non-limiting combinations include the combination of Si3N4 and TiO2, the combination of Si3N4 and ZnSnO x , the combination of Si3N4 and ZrO2, the combination of ZnSnO x and NbO y , the combination of ZnSnO x and TaO, or the combination of Si3N4, TiO2, ZnSnO x , ZrO2 and TaO.

[0017] Among them, 0 < x ≤ 2, for example, it can be 0.1, 0.2, 0.5, 1, 1.5 or 2, but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0018] 0 < y ≤ 2, for example, it can be 0.1, 0.2, 0.5, 1, 1.5 or 2, but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0019] Preferably, the thickness of the dielectric layer is 20 nm - 50 nm, for example, it can be 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm or 50 nm, but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0020] Preferably, the material of the first crystalline dielectric layer is Zn2SnO4 and / or Nb2O5.

[0021] Preferably, the material of the second crystalline dielectric layer is Zn2SnO4 and / or Nb2O5.

[0022] Preferably, the thickness of the first crystalline dielectric layer is 8 nm - 20 nm, for example, it can be 8 nm, 10 nm, 12 nm, 14 nm, 16 nm, 18 nm or 20 nm, but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0023] Preferably, the thickness of the silver layer is 5 nm - 20 nm, for example, it can be 5 nm, 8 nm, 10 nm, 12 nm, 14 nm, 16 nm, 18 nm or 20 nm, but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0024] Preferably, the thickness of the second crystalline dielectric layer is 8 nm - 20 nm, for example, it can be 8 nm, 10 nm, 12 nm, 14 nm, 16 nm, 18 nm or 20 nm, but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0025] Preferably, the material of the protective layer is any one or a combination of at least two of ZrO2, NbO a , SiC b , Si3N4, SiNC c or TiN d . Typical but non - restrictive combinations include the combination of ZrO2 and NbO a , the combination of SiC b and Si3N4, the combination of Si3N4 and SiNC c , the combination of SiNC c and TiN d , the combination of NbO a and SiC b , or the combination of ZrO2, NbO a , SiC b , Si3N4 and TiN d .

[0026] Among them, 0 < a ≤ 2. For example, it can be 0.1, 0.2, 0.5, 1, 1.5 or 2, but not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0027] 0 < b ≤ 4. For example, it can be 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5 or 4, but not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0028] 0 < c ≤ 4. For example, it can be 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5 or 4, but not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0029] 0 < d ≤ 4. For example, it can be 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5 or 4, but not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0030] Preferably, the thickness of the protective layer is 5 nm - 15 nm. For example, it can be 5 nm, 8 nm, 10 nm, 12 nm, 14 nm or 15 nm, but not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0031] The function of the protective layer in the present invention is to ensure the quality of the film surface during the later processing of the coated glass, such as hot bending, bending steel, laminating, etc.

[0032] In a second aspect, the present invention provides a method for preparing a multi - silver - layer low - emissivity coated glass containing a crystalline dielectric layer as described in the first aspect. The preparation method includes the following steps:

[0033] Adopt the vacuum magnetron sputtering coating method to deposit a dielectric layer, at least three continuously arranged composite low - emissivity functional layers, a dielectric layer and a protective layer on the glass substrate.

[0034] Preferably, the preparation method further includes a heat treatment process for the coated glass.

[0035] The heat treatment method in the present invention includes heat - treating the coated glass or separately and independently heat - treating the first crystalline dielectric layer and the second crystalline dielectric layer. The method for heat - treating the coated glass includes substrate heating or toughening heat treatment; the method for separately and independently heat - treating the first crystalline dielectric layer and the second crystalline dielectric layer includes laser treatment and / or irradiation treatment. The substrate heating in the present invention is carried out before the deposition of the coated glass, and the laser treatment, radiation treatment and toughening heat treatment are carried out after the deposition.

[0036] The temperature of the heat-treated coated glass is 500 - 720 °C. For example, it can be 500 °C, 550 °C, 600 °C, 650 °C, 700 °C or 720 °C, but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0037] The temperature for heat-treating the first crystalline dielectric layer is 500 - 720 °C. For example, it can be 500 °C, 550 °C, 600 °C, 650 °C, 700 °C or 720 °C, but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0038] The temperature for heat-treating the second crystalline dielectric layer is 500 - 720 °C. For example, it can be 500 °C, 550 °C, 600 °C, 650 °C, 700 °C or 720 °C, but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0039] The purpose of the heat treatment in the present invention is to transform the sputtered amorphous material into a crystalline stable structure.

[0040] Preferably, the dielectric layer is sputtered by a target of an alternating current cathode in an argon-nitrogen atmosphere or an argon-oxygen atmosphere.

[0041] Preferably, the composite low-emissivity functional layer is deposited by successively depositing a first crystalline dielectric layer, a silver layer, and a second crystalline dielectric layer.

[0042] Preferably, the first crystalline dielectric layer is sputtered by an oxidized ceramic target of an alternating current cathode in an argon atmosphere.

[0043] Preferably, the silver layer is sputtered by a direct current flat silver target in an argon atmosphere.

[0044] Preferably, the second crystalline dielectric layer is sputtered by an oxidized ceramic target of an alternating current cathode in an argon atmosphere.

[0045] Preferably, the protective layer is sputtered by an alternating current round target in an argon atmosphere or an argon-nitrogen atmosphere.

[0046] In a third aspect, the present invention provides the use of the multi-silver layer low-emissivity coated glass containing a crystalline dielectric layer as described in the first aspect. The multi-silver layer low-emissivity coated glass containing a crystalline dielectric layer can not only be used as building energy-saving glass, but also be used on the laminated glass for the front windshield of an automobile, playing the role of energy conservation and environmental protection.

[0047] The numerical range described in the present invention not only includes the above-listed point values, but also includes any point values between the above numerical ranges that are not listed. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.

[0048] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0049] The multi-silver-layer low-emissivity coated glass containing a crystalline dielectric layer provided by the present invention has a unique film layer structure, improves the traditional low-emissivity coated glass, and solves the problem of reduced visible light transmittance of the traditional low-emissivity coated glass after the number of silver layers increases. In particular, the use of a crystalline dielectric layer instead of the barrier protection of the dielectric layer improves the service life of the coated glass. The multi-silver-layer low-emissivity coated glass provided by the present invention has a high visible light transmittance, a low emissivity, a good light-to-heat ratio, good corrosion resistance, and can be bent and tempered at the same time, which can meet the requirements of the automotive field for coated glass and is more suitable for market demand. Detailed implementation manners

[0050] The technical solution of the present invention will be further described below through specific implementation manners. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0051] Embodiment 1

[0052] This embodiment provides a multi-silver-layer low-emissivity coated glass containing a crystalline dielectric. The film layer structure of the multi-silver-layer low-emissivity coated glass from the glass substrate outwards includes: a glass substrate, 3 continuously arranged composite low-emissivity functional layers, and a protective layer;

[0053] One dielectric layer is provided on each of the inner and outer sides of the composite low-emissivity functional layer;

[0054] The 3 continuously arranged composite low-emissivity functional layers include a first composite low-emissivity functional layer, a second composite low-emissivity functional layer, and a third composite low-emissivity functional layer;

[0055] The first composite low-emissivity functional layer, the second composite low-emissivity functional layer, and the third composite low-emissivity functional layer each independently include a first crystalline dielectric layer, a silver layer, and a second crystalline dielectric layer;

[0056] The material composition and film layer thickness of each film layer of the coated glass from the glass substrate outwards are shown in Table 1.

[0057] The magnetron sputtering coating machine specifically used in this embodiment includes 23 AC cathodes and 8 DC planar cathodes. Using the process parameters listed in Table 1, 11 AC circular targets and 3 DC single targets, a total of 14 target positions are used for production, and the coating is carried out in sequence according to the order of the film layers to produce the multi-silver-layer low-emissivity coated glass containing a crystalline dielectric described in this embodiment. The glass substrate needs to be cleaned and dried before coating, and then undergoes a pre-vacuum transition in a vacuum magnetron sputtering coating machine, and then the coating process starts. Its process parameters and the positions of the targets are shown in Table 1.

[0058] The preparation method further includes heating the coated glass to 550 °C by heating the substrate before depositing all the crystalline dielectric layers, so that the deposited material is transformed from amorphous state to crystalline state.

[0059] Table 1

[0060]

[0061] According to the above film system structure and production method, a triple-silver layer low-emissivity coating containing a crystalline dielectric layer was prepared on a 6-mm glass substrate. After testing, the emissivity ε of the coated glass obtained in this example is 0.015, SHGC = 0.36, and Tv (visible light transmittance) = 76%.

[0062] Refer to GB / T 18951.1 to conduct acid and alkali resistance experiments on the triple-silver layer low-emissivity coated glass containing a crystalline dielectric layer prepared in this example. Immerse the coated glass in 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide solution respectively. After 4 hours, obvious film layer peeling phenomenon occurred on the glass in the hydrochloric acid solution, and there was no obvious film layer peeling on the glass in the sodium hydroxide solution after 24 hours.

[0063] Example 2

[0064] This example provides a multi-silver layer low-emissivity coated glass containing a crystalline dielectric. The film layer structure of the multi-silver layer low-emissivity coated glass from the glass substrate outwards includes: a glass substrate, 4 continuously arranged composite low-emissivity functional layers, and a protective layer;

[0065] One dielectric layer is arranged on each of the inner and outer sides of the composite low-emissivity functional layer;

[0066] The 4 continuously arranged composite low-emissivity functional layers include a first composite low-emissivity functional layer, a second composite low-emissivity functional layer, a third composite low-emissivity functional layer, and a fourth composite low-emissivity functional layer;

[0067] The first composite low-emissivity functional layer, the second composite low-emissivity functional layer, the third composite low-emissivity functional layer, and the fourth composite low-emissivity functional layer each independently include a first crystalline dielectric layer, a silver layer, and a second crystalline dielectric layer;

[0068] The material composition and film layer thickness of each film layer of the coated glass from the glass substrate outwards are shown in Table 2.

[0069] The magnetron sputtering coating machine specifically used in this embodiment includes 23 AC cathodes and 8 DC planar cathodes. Using the process parameters listed in Table 2, 14 AC circular targets and 4 DC single targets are used, and a total of 18 target positions are used for production. Coating is carried out in sequence according to the order of the film layers to produce the multi-silver layer low-emissivity coated glass containing crystalline medium described in this embodiment. The glass substrate needs to be cleaned and dried before coating, and then undergoes a pre-vacuum transition in a vacuum magnetron sputtering coating machine, and then the coating process begins. Its process parameters and the positions of the targets are shown in Table 2.

[0070] The preparation method further includes, after coating, heating the first crystalline medium layer and the second crystalline medium layer to 680 °C by means of tempered heat treatment and holding for 2 - 3 minutes, so that the materials of all the crystalline medium layers are transformed from amorphous state to crystalline state.

[0071] Table 2

[0072]

[0073] According to the above film system structure and production method, a four-silver layer low-emissivity coating containing a crystalline medium layer is prepared on a 6 mm glass substrate. After testing, the emissivity ε of the coated glass obtained in this embodiment is 0.010, SHGC = 0.33, and Tv (visible light transmittance) = 68%.

[0074] Referring to GB / T 18951.1, the acid resistance and alkali resistance experiments are carried out on the four-silver layer low-emissivity coated glass containing a crystalline medium layer prepared in this embodiment. The coated glass is respectively immersed in 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide solution. The film layer on the glass in the hydrochloric acid solution begins to show obvious peeling after 3 hours, and the film layer on the glass in the sodium hydroxide solution shows no obvious peeling after 24 hours.

[0075] Example 3

[0076] This embodiment provides a multi-silver layer low-emissivity coated glass. Except that the materials of the first crystalline medium layer and the second crystalline medium layer in the composite low-emissivity functional layer are replaced with Nb2O5, and the heat treatment process is changed to laser heating the first crystalline medium layer and the second crystalline medium layer to 500 °C, the rest are the same as in Example 1.

[0077] According to the above film system structure and production method, a three-silver layer low-emissivity coating containing a crystalline medium layer is prepared on the glass substrate. After testing, the emissivity ε of the coated glass obtained in this embodiment is 0.016, SHGC = 0.36, and Tv (visible light transmittance) = 74%.

[0078] Referring to GB / T 18951.1, the acid resistance and alkali resistance tests were carried out on the three-silver layer low-emissivity coated glass with a crystalline dielectric layer prepared in this example. The coated glass was immersed in 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide solution respectively. After 3 hours, the film layer on the glass in the hydrochloric acid solution began to show obvious peeling phenomenon, and there was no obvious peeling of the film layer on the glass in the sodium hydroxide solution after 24 hours.

[0079] Comparative Example 1

[0080] This comparative example provides a multi-silver layer low-emissivity coated glass. Except that the first crystalline dielectric layer and the second crystalline dielectric layer in the composite low-emissivity functional layer are both replaced with dielectric layers, the rest are the same as in Example 1.

[0081] Taking the first composite low-emissivity functional layer as an example, the first crystalline dielectric layer in it was replaced with a dielectric layer with a thickness of 10 nm and a material of AZO; the second crystalline dielectric layer in it was replaced with a dielectric layer with a thickness of 10 nm and a material of AZO.

[0082] According to the above film system structure and production method, a three-silver layer low-emissivity coating containing a crystalline dielectric layer was prepared on a 6 mm glass substrate. After testing, the emissivity ε of the coated glass obtained in this comparative example was 0.014, SHGC was 0.36, and Tv (visible light transmittance) was 75%.

[0083] Referring to GB / T 18951.1, the acid resistance and alkali resistance tests were carried out on the three-silver layer low-emissivity coated glass prepared in this comparative example. The coated glass was immersed in 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide solution respectively. After 5 minutes, the film layer on the glass in the hydrochloric acid solution had completely peeled off, and obvious film layer peeling began on the glass in the sodium hydroxide solution after 8 hours.

[0084] Compared with Example 1, the visible light transmittance and emissivity of the coated glass obtained in this comparative example are similar to those of the coated glass prepared in Example 1, but the corrosion resistance is much worse than that of Example 1.

[0085] Comparative Example 2

[0086] This comparative example provides a multi-silver layer low-emissivity coated glass. Except that the first crystalline dielectric layer and the second crystalline dielectric layer in the composite low-emissivity functional layer are both replaced with the ordinary dielectric layer AZO, the rest are the same as in Example 2.

[0087] Taking the first composite low-emissivity functional layer as an example, the first crystalline dielectric layer in it was replaced with a dielectric layer with a thickness of 12 nm and a material of AZO; the second crystalline dielectric layer in it was replaced with a dielectric layer with a thickness of 12 nm and a material of AZO.

[0088] According to the above film system structure and production method, a four-silver-layer low-emissivity coating containing a crystalline dielectric layer was prepared on a 6-mm glass substrate. After testing, the emissivity ε of the coated glass obtained in this comparative example was 0.009, SHGC = 0.33, and Tv (visible light transmittance) = 65%.

[0089] Referring to GB / T 18951.1, acid resistance and alkali resistance tests were carried out on the four-silver-layer low-emissivity coated glass prepared in this comparative example. The coated glass was immersed in 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide solution respectively. After 5 minutes, the film layer on the glass in the hydrochloric acid solution had completely peeled off, and obvious film layer peeling began to occur on the glass in the sodium hydroxide solution after 5 hours.

[0090] Compared with Example 2, the visible light transmittance and emissivity of the coated glass obtained in this comparative example were similar to those of the coated glass prepared in Example 2, but the corrosion resistance was much worse than that of Example 2.

[0091] Comparative Example 3

[0092] This comparative example provides a multi-silver-layer low-emissivity coated glass. Except that the second crystalline dielectric layer of the composite low-emissivity functional layer is replaced with a metal barrier layer NiCr, the rest are the same as in Example 1.

[0093] Taking the first composite low-emissivity functional layer as an example, the second crystalline dielectric layer therein was replaced with a metal barrier layer with a thickness of 3 nm and a material of NiCr.

[0094] According to the above film system structure and production method, a three-silver-layer low-emissivity coating containing a crystalline dielectric layer was prepared on a glass substrate. After testing, the emissivity ε of the coated glass obtained in this comparative example was 0.015, SHGC = 0.34, and Tv (visible light transmittance) = 69%.

[0095] Referring to GB / T 18951.1, acid resistance and alkali resistance tests were carried out on the coated glass prepared in this comparative example. The coated glass was immersed in 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide solution respectively. After 4 hours, obvious film layer peeling began to occur on the glass in the hydrochloric acid solution, and there was no obvious film layer peeling on the glass in the sodium hydroxide solution after 24 hours.

[0096] Compared with Example 1, the emissivity of the coated glass obtained in this comparative example was the same as that of Example 1, and the acid and alkali resistance of the film layer was also similar to that of Example 1, but the visible light transmittance was much worse than that of Example 1.

[0097] Comparative Example 4

[0098] This comparative example provides a multi-silver-layer low-emissivity coated glass. Except that the first crystalline dielectric layer and the second crystalline dielectric layer of the composite low-emissivity layer are both replaced with metal barrier layers, the rest are the same as in Example 1.

[0099] Taking the first composite low-emissivity functional layer as an example, the first crystalline dielectric layer therein is replaced with a metal barrier layer with a thickness of 3 nm and a material of NiCr; the second crystalline dielectric layer therein is replaced with a metal barrier layer with a thickness of 3 nm and a material of NiCr.

[0100] According to the above film system structure and production method, a three-silver-layer low-emissivity coating containing a crystalline dielectric layer is prepared on a glass substrate. After testing, the emissivity ε of the coated glass obtained in this comparative example is 0.018, SHGC = 0.31, and Tv (visible light transmittance) = 63%.

[0101] Referring to GB / T 18951.1, the acid resistance and alkali resistance experiments are carried out on the three-silver-layer low-emissivity coated glass prepared in this comparative example. The coated glass is respectively immersed in 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide solution. The film layer on the glass in the hydrochloric acid solution begins to fall off after 12 hours, and there is no obvious film layer falling off phenomenon on the glass in the sodium hydroxide solution after 24 hours.

[0102] Compared with Example 1, the acid and alkali resistance of the coated glass obtained in this comparative example is much better than that of Example 1, but the visible light transmittance, emissivity and shading performance are much worse than those of Example 1.

[0103] The visible light transmittance Tv%, emissivity ε, total solar energy transmittance SHGC, acid resistance time and alkali resistance time of the coated glass prepared by using the methods described in Examples 1-3 and Comparative Examples 1-4 are shown in Table 3.

[0104] Table 3

[0105]

[0106] As can be seen from Table 3, the multi-silver-layer low-emissivity coated glass containing a crystalline dielectric layer described in the present invention has excellent visible light transmittance Tv%, emissivity ε, total solar energy transmittance SHGC, acid resistance and alkali resistance. Compared with the comparative examples, Example 1 has better acid resistance and alkali resistance; compared with Comparative Examples 3-4, Example 1 has better visible light transmittance Tv%; compared with Comparative Example 2, Example 2 has better total solar energy transmittance SHGC, acid resistance and alkali resistance.

[0107] In summary, the multi-silver-layer low-emissivity coated glass containing a crystalline dielectric layer provided by the present invention has a high visible light transmittance, a low emissivity, a good light-to-heat ratio, good corrosion resistance, and can be bent and tempered, which can meet the requirements of the automotive field and the construction industry for coated glass and is more suitable for the market demand.

[0108] The specific embodiments described above have further elaborated on the purpose, technical solutions, and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not used to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A multi - silver - layer low - emissivity coated glass with a crystalline dielectric layer and an emissivity ≤ 0.018, characterized in that, The film layer structure of the multi-silver layer low-emissivity coated glass containing a crystalline dielectric layer is sequentially arranged from the glass substrate outwards as follows: glass substrate, dielectric layer, composite low-emissivity functional layer, dielectric layer, composite low-emissivity functional layer, dielectric layer, composite low-emissivity functional layer, dielectric layer, protective layer; The composite low-emissivity functional layer is sequentially a first crystalline dielectric layer, a silver layer and a second crystalline dielectric layer stacked along the direction outwards from the glass substrate; The material of the dielectric layer is any one or a combination of at least two of Si3N4, TiO2, ZrO2 or TaO; The materials of the first crystalline dielectric layer and the second crystalline dielectric layer are Zn2SnO4 and / or Nb2O5; The multi-silver layer low-emissivity coated glass is prepared by the following method, and the method includes: Adopting a vacuum magnetron sputtering coating method to deposit a dielectric layer, at least three continuously arranged composite low-emissivity functional layers, a dielectric layer and a protective layer on the glass substrate; Among them, depositing the composite low-emissivity functional layer is to sequentially deposit a first crystalline dielectric layer, a silver layer and a second crystalline dielectric layer; both the first crystalline dielectric layer and the second crystalline dielectric layer are sputtered by an AC cathode oxidation ceramic target in an argon atmosphere; the silver layer is sputtered by a DC flat silver target in an argon atmosphere.

2. The multi-silver layer low-emissivity coated glass containing a crystalline dielectric layer according to claim 1, characterized in that, The thickness of the first crystalline dielectric layer is 8 nm - 20 nm.

3. The multi-silver layer low-emissivity coated glass containing a crystalline dielectric layer according to claim 1, characterized in that, The thickness of the silver layer is 5 nm - 20 nm.

4. The multi-silver layer low-emissivity coated glass containing a crystalline dielectric layer according to claim 1, characterized in that, The thickness of the second crystalline dielectric layer is 8 nm - 20 nm.

5. The multi-silver layer low-emissivity coated glass containing a crystalline dielectric layer according to claim 1, wherein The material of the protective layer includes ZrO2, NbO a 、SiC b 、Si3N4、SiNC c or TiN d Any one or a combination of at least two of <a≤2,0<b≤4,0<c≤4,0<d≤4。 6. The multi-silver layer low-emissivity coated glass containing a crystalline dielectric layer according to claim 1, wherein, The thickness of the protective layer is 5 nm - 15 nm.

7. The multi-silver layer low-emissivity coated glass containing a crystalline dielectric layer according to claim 1, characterized in that, The material of the dielectric layer includes any one or a combination of at least two of Si3N4, TiO2, ZnSnO x , ZrO2, NbO y or TaO, where 0 < x ≤ 2 and 0 < y ≤ 2.

8. The multi-silver layer low-emissivity coated glass containing a crystalline dielectric layer according to claim 1, wherein The thickness of the dielectric layer is 20 nm - 50 nm.

9. A method for preparing a multi-silver layer low-emissivity coated glass containing a crystalline dielectric layer as described in claims 1-8, characterized in that, The preparation method includes the following steps: Adopting a vacuum magnetron sputtering coating method to deposit a dielectric layer, at least three continuously arranged composite low-emissivity functional layers, a dielectric layer and a protective layer on the glass substrate.

10. The preparation method according to claim 9, characterized in that, The preparation method further includes a heat treatment process for the coated glass.

11. The preparation method according to claim 10, characterized in that, The methods used in the heat treatment process of the coated glass include substrate heating, toughened heat treatment, laser treatment or irradiation treatment.

12. The preparation method according to claim 9, characterized in that, Depositing the composite low-emissivity functional layer is to sequentially deposit a first crystalline dielectric layer, a silver layer and a second crystalline dielectric layer.

13. The preparation method according to claim 9, characterized in that, The first crystalline dielectric layer is sputtered by an AC cathode oxidation ceramic target in an argon atmosphere.

14. The preparation method according to claim 9, characterized in that, The silver layer is sputtered by a DC flat silver target in an argon atmosphere.

15. The preparation method according to claim 9, wherein, The second crystalline dielectric layer is sputtered by an AC cathode oxidation ceramic target in an argon atmosphere.

16. Use of a multi-silver layer low-emissivity coated glass containing a crystalline dielectric layer as described in any one of claims 1-8, characterized in that, The multi-silver layer low-emissivity coated glass containing a crystalline dielectric layer is used as automotive front windshield laminated glass or building energy-saving glass.

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