Low-radiation easy-to-clean glass and multi-layer glass thereof

Abstract

The utility model relates to low-radiation easy-to-clean glass and multi-layer glass thereof. According to the low-radiation easy-to-clean glass, a silicon oxide target material is sputtered by radio frequency, gas nitrogen is introduced, and a silver target material is sputtered by direct current, so that nitrogen-doped silicon silver oxide is deposited on a clear glass base layer in a mixed plating manner. Therefore, according to the low-radiation easy-to-clean glass, the oxidation problem can be avoided, meanwhile, the electric conductivity, the hardness and the water drop angle are improved, and the hemispherical radiance is reduced.

Description

Technical Field

[0001] The present application relates to a glass, in particular to a low-radiation easy-to-clean glass and a composite glass thereof. Background Art

[0002] Low-E glass (Low-Emissivity Glass) is a type of coated glass. Emissivity is the ability of an object to absorb heat and then radiate it away. Low-E glass is primarily used in buildings to separate indoor and outdoor windows, thereby retaining indoor heat or reflecting outdoor heat, further reducing air conditioning energy use.

[0003] Of the energy in typical sunlight, infrared rays account for approximately 51.2% of heat, visible light for approximately 46.8%, and ultraviolet rays and other radiation for approximately 2%. Low-E glass primarily blocks infrared and ultraviolet rays within sunlight through a metallic dielectric coating. The blocking rate in the visible light region between 380nm and 760nm is very low, thus ensuring excellent light transmission. By blocking heat from entering a room, it reduces energy consumption for indoor air conditioning. Furthermore, significantly reducing ultraviolet transmittance significantly increases building comfort. Traditional coated and tinted glass, on the other hand, primarily reflects and absorbs visible light.

[0004] In other words, while the Low-E coating transmits up to 80% of visible light, its surface metal molecules reflect far-infrared rays, the primary heat-transmitting component of visible light, at a reflectivity of 70% to 90%. This significantly improves its optical performance compared to ordinary glass, effectively resolving the traditional conflict between thermal insulation and optical absorption. Low-E glass is primarily used in residential buildings for standard doors and windows, skylights, floor-to-ceiling windows, aluminum doors and windows, airtight windows, and curtain windows. Some companies also use it in various sunshades, achieving excellent results.

[0005] Taking the sputtering method as an example, Low-E glass production process generally involves depositing a single layer or multiple layers of metals, alloys, or metal oxides on the glass surface to form a glass product. Metals include silver, copper, tin, etc.

[0006] However, prior Low-E glass generally suffers from shortcomings such as a single color, low oxidation resistance, and low damage resistance. Furthermore, prior silver-coated Low-E glass, when used alone, is susceptible to oxidation due to exposure to air, oxygen, and moisture, so it is often used in multiple layers or laminated layers.

[0007] For example, patent CN202849261U describes a seven-layer structure of corrosion-resistant, oxidation-resistant, single-silver, low-emissivity coated glass, which is deposited on the surface of a glass substrate in sequence from the bottom up: tin oxide, zinc oxide, nickel-chromium, silver, nickel-chromium, ceramic titanium oxide, and ceramic silicon nitride. In short, this patent uses dielectric layers as insulation, sandwiching the silver layers above and below, to create a seven-layer structure of corrosion-resistant, oxidation-resistant, single-silver, low-emissivity coated glass.

[0008] Another example is patent No. CN203284327U, which features a glass layer, a first dielectric layer, a second dielectric layer, a first shielding layer, a silver layer, a second shielding layer, and a third dielectric layer arranged in order from the inside out. This patent utilizes dielectric layers as insulation, sandwiching silver film layers above and below to achieve low-reflectivity, gold-colored, off-site, and steelable, offline Low-E coated glass.

[0009] There are patents such as CN202378343U, CN202378343U, CN202378343U, CN212982795U, and CN214083227U, which use dielectric layers as insulation to clamp silver film layers from top to bottom.

[0010] However, these prior art methods may cause adverse side effects such as decreased conductivity, decreased hardness, decreased water drop angle, and increased hemispherical emissivity of the Low-E glass.

[0011] In view of this, the prior art still needs to be improved. Summary of the Invention

[0012] To solve the above and other problems, the main purpose of this application is to provide a low-emissivity easy-to-clean glass to improve the prior art.

[0013] An object of the present application is to provide a low-emissivity, easy-to-clean glass that has improved electrical conductivity compared to prior art.

[0014] Another object of the present application is to provide a low-emissivity, easy-to-clean glass that has higher hardness than the prior art.

[0015] Another object of the present application is to provide a low-emissivity, easy-to-clean glass that can improve the water drop angle compared to the prior art.

[0016] Another object of the present application is to provide a low-emissivity, easy-to-clean glass that can reduce hemispherical emissivity compared to prior art.

[0017] Another object of the present application is to provide a low-emissivity, easy-to-clean glass that can improve conductivity, hardness, water drop angle, and reduce hemispherical emissivity while avoiding oxidation problems.

[0018] To achieve the aforementioned and other objectives of the invention, an embodiment of the present application provides a method for manufacturing low-radiation, easy-to-clean glass, comprising: utilizing radio frequency sputtering of a silicon oxide target while simultaneously introducing nitrogen gas, and utilizing direct current sputtering of a silver target to deposit nitrogen-doped silicon oxide silver on a clear glass substrate by mixed plating.

[0019] Preferably, the method further comprises: annealing to obtain a low-emissivity easy-to-clean glass, wherein the low-emissivity easy-to-clean glass has a nitrogen-doped silver silicon oxide thin film stacked on the clear glass base layer.

[0020] Preferably, the method further comprises: again using RF sputtering to sputter the silicon oxide target while introducing nitrogen gas, and simultaneously using DC sputtering to sputter the silver target to deposit another nitrogen-doped silicon oxide silver (.

[0021] Preferably, the method further comprises: annealing again to obtain a low-emissivity easy-to-clean glass having two layers of nitrogen-doped silver silicon oxide thin films stacked.

[0022] Preferably, the annealing step comprises: introducing oxygen and performing annealing.

[0023] Preferably, the clear glass substrate is 5 mm thick.

[0024] Preferably, the hardness of the low-emissivity easy-to-clean glass is greater than 2H, and the contact angle is greater than 103 degrees.

[0025] Preferably, the hardness of the low-emissivity easy-to-clean glass is greater than 5H, and the contact angle is greater than 110 degrees.

[0026] Preferably, the method further comprises: maintaining the vacuum degree at 2x10 before sputtering. -6 mmHg or less.

[0027] Preferably, the working pressure of the nitrogen gas introduced during sputtering is maintained at 3.5-3.7 x 10 -3 mmHg.

[0028] To achieve the aforementioned and other purposes of the invention, the present invention further provides a low-emissivity, easy-to-clean glass, comprising: a first nitrogen-doped silver silicon oxide layer; and a glass layer, wherein the first nitrogen-doped silver silicon oxide layer is mixedly deposited on the glass layer using a low-emissivity, easy-to-clean glass manufacturing method.

[0029] Preferably, a second nitrogen-doped silver silicon oxide layer is further included, and the second nitrogen-doped silver silicon oxide layer (22) is deposited on the first nitrogen-doped silver silicon oxide layer by mixed plating.

[0030] Preferably, the glass layer is 5 mm thick.

[0031] Preferably, the hardness of the low-emissivity easy-to-clean glass is greater than 2H, and the contact angle is greater than 103 degrees.

[0032] Preferably, the hardness of the low-emissivity easy-to-clean glass is greater than 5H, and the contact angle is greater than 110 degrees.

[0033] Preferably, it further includes: a first transparent substrate layer; a second transparent substrate layer; a near-infrared light shielding layer, arranged between the first transparent substrate layer and the second transparent substrate layer, the near-infrared light shielding layer being formed by a plurality of tungsten oxide-containing nanoparticles distributed and fixed on polyethylene terephthalate; a first protective layer, arranged between the first transparent substrate layer and the near-infrared light shielding layer, the first protective layer being a polyethylene terephthalate layer; and, a second protective layer, arranged between the second transparent substrate layer and the near-infrared light shielding layer, the second protective layer being a polyethylene terephthalate layer.

[0034] Preferably, the first transparent substrate layer and the second transparent substrate layer are glass.

[0035] To achieve the above and other purposes, the embodiments of the present application further provide a low-emissivity, easy-to-clean, multi-layer glass, comprising: a first glass layer, the first glass layer being the low-emissivity, easy-to-clean glass as described above; a second glass layer; and an isolation frame, the first glass layer and the second glass layer being connected by the isolation frame.

[0036] Preferably, there is a hollow layer between the first glass layer and the second glass layer.

[0037] Preferably, the second glass layer is the aforementioned low-emissivity easy-to-clean glass.

[0038] In addition, directions or similar terms described herein, such as front, back, left, right, top, bottom, inside, outside, and side, are primarily used with reference to the directions in the drawings and are intended only to facilitate description and understanding of the various embodiments of the present invention and are not intended to limit the present invention. Furthermore, the use of articles such as a or the used herein to refer to components or members is intended only to simplify the description and should be interpreted as including one or at least one in the present invention, and the singular concept also includes the plural, unless otherwise apparent. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 It is a schematic diagram of a sputtering system of an embodiment.

[0040] Figure 2 This is the low-emissivity easy-to-clean glass of the embodiment.

[0041] Figure 3 This is another embodiment of low-emissivity easy-to-clean glass.

[0042] Figure 4 This is the low-emissivity easy-to-clean double-layer glass of the embodiment of the present application.

[0043] Symbol Marking Description

[0044] 10: Glass layer 21: First nitrogen-doped silver silicon oxide layer 22: Second nitrogen-doped silver silicon oxide layer

[0045] 31: First transparent substrate layer

[0046] 32: Second transparent substrate layer

[0047] 40: Near infrared light shielding layer

[0048] 51: First protective layer

[0049] 52: Second protective layer

[0050] 71: First glass layer

[0051] 72: Second glass layer

[0052] 73: Isolation box

[0053] 91: Sputtering gun

[0054] 92: Sputtering base

[0055] 93: Sputtering turntable

[0056] 94: Pump

[0057] 95: Gas cylinder

[0058] 96: Radio Frequency (RF) Generator

[0059] 97: DC generator DETAILED DESCRIPTION

[0060] In order to make the above and other purposes, features and advantages of this application more clearly understood, preferred embodiments are given below and described in detail with reference to the accompanying drawings. Items marked with the same symbols in different drawings may be considered the same and their descriptions may be omitted.

[0061] There are two common coating methods for Low-E coated glass: hard coating and soft coating.

[0062] Hard Low-E glass can be produced in single-piece, laminated, or multi-layer configurations, and can be directly tempered and bent at high temperatures, making it extremely convenient to use. Its manufacturing method primarily utilizes a pyrolytic process. After the glass paste leaves the furnace, a Low-E film material is sprayed onto the formed, high-temperature flat glass. This pyrolytic process coats the film material onto the flat glass. Because this Low-E coating method is inline with the glass manufacturing process, it is also known as in-line Low-E glass.

[0063] Soft Low-E Glass is not suitable for long-term exposure to air because its metal coating is not heat-resistant and easily oxidizes. However, its excellent thermal insulation makes it a good choice for composite glass. Its manufacturing method uses a vacuum coating process, or sputtering or magnetron sputtering on flat glass to deposit multiple layers of metal or ceramic thin films. This is also known as linear-coated Low-E glass.

[0064] This embodiment provides a method for producing low-emissivity, easy-to-clean glass. The method includes using radio frequency (RF) sputtering of a silicon oxide target while simultaneously introducing nitrogen gas, and simultaneously using direct current (DC) sputtering of a silver target to deposit nitrogen-doped silicon oxide silver (Si, O, N:Ag) onto a glass substrate. This method avoids oxidation while improving conductivity, hardness, and water drop angle, and reducing hemispherical emissivity.

[0065] In a vacuum, high-energy positive ions, accelerated by a high-voltage electric field, collide with a solid surface. Atoms and molecules on the solid surface exchange kinetic energy with these high-energy incident particles, causing them to be liberated from the solid surface. This phenomenon is called sputtering. If the sputtered atoms reach the substrate surface and deposit a thin film, the process is called sputtering.

[0066] In a DC sputtering system, if the target to be sputtered is an insulator, the target surface, due to its poor conductivity and the constant bombardment of positive charges, will gradually accumulate positive charges. As the amount of positive charge accumulates on the target surface, its potential continues to rise until it reaches zero, and the glow discharge phenomenon disappears, making it difficult to sputter materials with low conductivity. An AC power supply can solve this problem. By alternating between positive and negative voltages, the accumulated positive charge on the target surface is neutralized by electrons. However, if the AC power supply frequency is not high enough, and the half-cycle is too short to neutralize the accumulated charge on the target surface, the glow discharge will not last long. In this case, using an RF power supply that switches the AC current between positive and negative at a frequency greater than 1MHz can eliminate the charge accumulation problem, even if the target is non-conductive.

[0067] Figure 1 Schematic diagram of a sputtering system according to an embodiment of the present invention. The sputtering system mainly includes a sputtering gun 91 , a sputtering base 92 , a sputtering turntable 93 , a pump 94 , a gas cylinder 95 , a radio frequency (RF) generator 96 , and a direct current (DC) generator 97 .

[0068] First, prepare a silicon oxide target, a silver target, a glass substrate (Corning glass, 5 mm thick), and nitrogen gas. Then, use a pump to evacuate to a vacuum of 2 x 10 -6The pressure of nitrogen gas introduced during sputtering is controlled at 3.5~3.7x 10 -3 mmHg, the working distance was 200 mm, the glass substrate rotation speed was 20 rpm, and the deposition time was fixed at 1 hour (hr).

[0069] The pump is preferably a mechanical pump or a turbo pump.

[0070] Preferably, the method for manufacturing low-emissivity, easy-to-clean glass of this embodiment further includes annealing to obtain the low-emissivity, easy-to-clean glass, wherein the low-emissivity, easy-to-clean glass comprises a nitrogen-doped silver silicon oxide (Si, O, N:Ag) thin film laminated on the glass substrate. The low-emissivity, easy-to-clean glass comprising a single layer of nitrogen-doped silver silicon oxide (Si, O, N:Ag) thin film exhibits a hardness greater than 2H and a contact angle greater than 103 degrees.

[0071] Generally speaking, sputtering without heating does not give the deposited particles sufficient kinetic energy to diffuse, and the particles are relatively unable to reach their intended positions in the structure, so a relatively complete crystalline structure cannot be formed. After annealing, the film can produce a thermal effect through annealing, which causes the atoms in the film to rearrange their lattice positions, thereby reducing defects in the crystal and enlarging the grains. This helps to improve the crystallinity of the film, making the film more dense, and can also activate carriers, increasing carrier concentration and electron mobility, thereby increasing conductivity.

[0072] Prior art annealing typically uses inert gases such as argon and nitrogen to reduce secondary reactions. Sometimes, forming gases, such as a mixture of hydrogen and nitrogen, are also used. The reducing power of hydrogen removes oxygen molecules from the film, reducing its oxygen content.

[0073] Preferably, the annealing step of this embodiment includes introducing oxygen gas for annealing. Thus, oxygen vacancies formed during sputtering not only rearrange the crystal lattice due to annealing, but also fill the vacancies during the oxygen gas annealing step, further reducing defects and achieving a more perfect structure, lowering binding energy, and improving conductivity.

[0074] Preferably, this embodiment can again utilize radio frequency (RF) sputtering of a silicon oxide target while simultaneously introducing nitrogen gas, and simultaneously utilize direct current (DC) sputtering of a silver target to achieve mixed deposition of another nitrogen-doped silver oxide (Si, O, N:Ag) silicon oxide. Subsequently, annealing is performed again to obtain a low-emissivity, easy-to-clean glass having two layers of nitrogen-doped silver oxide (Si, O, N:Ag) thin films stacked together. This results in a low-emissivity, easy-to-clean glass having a double layer of nitrogen-doped silver oxide (Si, O, N:Ag) thin films stacked together. The low-emissivity, easy-to-clean glass having a double layer of nitrogen-doped silver oxide (Si, O, N:Ag) thin films exhibits a hardness greater than 5H and a contact angle greater than 110 degrees.

[0075] Figure 2 Low-emissivity easy-to-clean glass of the embodiment. Figure 3 This is another embodiment of low-emissivity easy-to-clean glass.

[0076] like Figure 2 As shown, the low-emissivity, easy-to-clean glass of this embodiment comprises: a first nitrogen-doped silver silicon oxide layer 21; and a glass substrate 10, on which the first nitrogen-doped silver silicon oxide layer 21 is deposited by mixed plating. The low-emissivity, easy-to-clean glass has a hardness greater than 2H and a contact angle greater than 103 degrees.

[0077] Preferably, the low-emissivity easy-to-clean glass of this embodiment may further include a second nitrogen-doped silver silicon oxide layer 22, which is deposited on the first nitrogen-doped silver silicon oxide layer 21. Figure 1 The double-layer nitride-doped silver silicon oxide (Si, O, N:Ag) film of low-emissivity, easy-to-clean glass has a hardness greater than 5H and a contact angle greater than 110 degrees.

[0078] Preferably, the glass layer 10 is 5 mm thick. Of course, 1.7 mm, 6 mm, and 8 mm are all common choices.

[0079] like Figure 3 As shown, another embodiment of the low-emissivity easy-to-clean glass includes: a first nitrogen-doped silver silicon oxide layer 21; a second nitrogen-doped silver silicon oxide layer 22, the second nitrogen-doped silver silicon oxide layer 22 is mixedly deposited on the first nitrogen-doped silver silicon oxide layer 21; and a glass substrate 10, the first nitrogen-doped silver silicon oxide layer 21 is mixedly deposited on the glass substrate 10.

[0080] The glass substrate 10 of another embodiment includes: a first transparent substrate layer 31; a second transparent substrate layer 32; a near-infrared light shielding layer 40 disposed between the first transparent substrate layer 31 and the second transparent substrate layer 32, wherein the near-infrared light shielding layer 40 is formed by a plurality of tungsten oxide-containing nanoparticles distributed and fixed on polyethylene terephthalate (PET); a first protective layer 51 disposed between the first transparent substrate layer 31 and the near-infrared light shielding layer 40, wherein the first protective layer 51 is a polyethylene terephthalate layer; and a second protective layer 52 disposed between the second transparent substrate layer 32 and the near-infrared light shielding layer 40, wherein the second protective layer 52 is a polyethylene terephthalate layer.

[0081] Preferably, the first transparent substrate layer 31 and the second transparent substrate layer 32 are made of glass.

[0082] Table 1 shows the relevant data of the comparative examples and embodiments.

[0083] Test items Comparative Example 1 Comparative Example 2 Example 1 Example 2 Hemispherical emissivity 0.88 0.176 0.25 0.21 hardness 9H <6B 5～6H 2～3H Water drop corner 16 67 110 103 Base plate(5mm) Clear glass Single-layer silver-plated glass Single-layer silver glass Double silver glass

[0084] Table 1

[0085] In summary, compared to the glass of the prior art, which has the adverse side effects of decreased conductivity, decreased hardness, decreased water drop angle, and increased hemispherical emissivity, the embodiments of the present application provide a method for manufacturing low-emissivity, easy-to-clean glass and its low-emissivity, which can avoid oxidation problems while improving conductivity, hardness, water drop angle, and reducing hemispherical emissivity.

[0086] In addition, if the thermal insulation effect is considered instead of the sound insulation effect, the low-emissivity easy-clean glass of the embodiment of the present application can be further applied to low-emissivity easy-clean composite glass.

[0087] Figure 4 This is the low-emissivity easy-to-clean double-layer glass of the embodiment of the present application. Figure 4 As shown, a low-emissivity easy-cleaning double-layer glass of this embodiment comprises: a first glass layer 71, which is the aforementioned low-emissivity easy-cleaning glass; a second glass layer 72; and an isolation frame 73, through which the first glass layer 71 and the second glass layer 72 are connected.

[0088] Preferably, a hollow layer 74 is formed between the first glass layer 71 and the second glass layer 72 .

[0089] Preferably, the second glass layer 72 is the aforementioned low-emissivity easy-to-clean glass.

[0090] Thereby, the present application not only improves the heat insulation effect, but also improves the sound insulation effect.

[0091] Although this application has been disclosed using the preferred embodiments described above, they are not intended to limit the present invention. Any person skilled in the art may make various changes and modifications to the above embodiments without departing from the spirit and scope of this application, and these changes and modifications are still within the scope of the technology protected by this application. Therefore, the scope of protection of this application shall include all changes within the meaning and equivalent scope of the appended claims. If the above embodiments can be combined, this application includes any combination of implementations.

Claims

1. A low-emissivity easy-to-clean glass, characterized in that: Include: a first nitrogen-doped silver silicon oxide layer (21); and A glass substrate (10) is provided on which the first nitrogen-doped silicon oxide silver layer (21) is deposited by mixed plating.

2. The low-emissivity easy-to-clean glass according to claim 1, wherein: The invention also comprises a second nitrogen-doped silver silicon oxide layer (22), wherein the second nitrogen-doped silver silicon oxide layer (22) is deposited on the first nitrogen-doped silver silicon oxide layer (21) by mixed plating.

3. The low-emissivity easy-to-clean glass according to claim 1 or 2, characterized in that: The hardness of the low-emissivity easy-to-clean glass is greater than 2H and the contact angle is greater than 103 degrees.

4. The low-emissivity easy-to-clean glass according to claim 1, wherein: The hardness of the low-emissivity easy-to-clean glass is greater than 5H and the contact angle is greater than 110 degrees.

5. The low-emissivity easy-to-clean glass according to claim 1, wherein: The glass substrate (10) comprises: a first transparent substrate layer (31); a second transparent substrate layer (32); a near-infrared light shielding layer (40) disposed between the first transparent substrate layer (31) and the second transparent substrate layer (32), wherein the near-infrared light shielding layer (40) is formed by distributing and fixing a plurality of nanoparticles containing tungsten oxide on polyethylene terephthalate; a first protective layer (51) disposed between the first transparent substrate layer (31) and the near-infrared light shielding layer (40), wherein the first protective layer (51) is a polyethylene terephthalate layer; and A second protective layer (52) is disposed between the second transparent substrate layer (32) and the near-infrared light shielding layer (40), and the second protective layer (52) is a polyethylene terephthalate layer.

6. The low-emissivity easy-to-clean glass according to claim 5, wherein: The first transparent substrate layer (31) and the second transparent substrate layer (32) are made of glass.

7. A low-emissivity easy-to-clean double-layer glass, characterized by: Include: a first glass layer (71), wherein the first glass layer (71) is the low-emissivity easy-to-clean glass as claimed in claim 1; a second glass layer (72); and An isolation frame (73), the first glass layer (71) and the second glass layer (72) are connected through the isolation frame (73).

8. The low-emissivity easy-to-clean double-glazing unit according to claim 7, wherein: A hollow layer (74) is provided between the first glass layer (71) and the second glass layer (72).

9. The low-emissivity easy-to-clean double-glazing unit according to claim 7, wherein: The second glass layer (72) is the low-emissivity easy-to-clean glass as claimed in claim 1.

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