CN108975726B - ultra-LOW reflection toughened LOW-E glass - Google Patents

Abstract

The invention relates to the technical field of glass production, in particular to ultra-LOW reflection toughened LOW-E glass, which comprises a glass substrate and a composite film layer plated on the surface of the glass substrate, wherein the composite film layer comprises a first dielectric layer, a transition layer, a first seed layer, a first functional layer, a first protection layer, a first AZO layer, a second dielectric layer, a second seed layer, a second functional layer, a second protection layer, a second AZO layer and a third dielectric layer which are plated outwards from the glass substrate in sequence, the first functional layer is a Cu layer, and the second functional layer is an Ag layer.

Description

Ultra-low reflective tempered LOW-E glass

Technical field

The invention relates to the technical field of glass production, and specifically relates to an ultra-low reflection temperable LOW-E glass.

Background technique

Low-radiation coated glass is a glass product with a low-radiation functional layer deposited on the surface of float glass. The low-radiation functional layer reflects the near-infrared rays in sunlight and the far-infrared rays in the living environment, thereby reducing the absorption and absorption of infrared rays by the glass. radiation. Low-emissivity coated glass can be used not only for home doors and windows, but also for glass curtain walls in shopping malls, office buildings, high-end hotels and other places where needed.

Traditional low-emissivity coated glass has a high reflectivity of visible light. With the large-scale use of low-emissivity coated glass, "light pollution" has become an urgent problem that plagues urban residents. In order to reduce this "light pollution" phenomenon caused by the large-scale use of glass curtain walls, local governments have promulgated policies and regulations to restrict the external reflection of building glass. For example, Shanghai stipulates that the external feedback must be less than 15%, and the external feedback involving residential areas is generally less than 7% to 11%, and the external feedback requirement for some projects is less than 5%.

At present, low-emissivity coated glass that can be heat treated at high temperatures can be bent, so it can better express the architectural design concept. On the other hand, it can also significantly reduce the cost of production and processing, so it is a more common type on the market. product. Although buildings using tempered coated glass have different colors when viewed from a distance, when viewed up close, they all appear to be a more obvious and uniform blue-green or yellow-green, which makes it difficult to demonstrate their advanced feel. The reason why the transmitted color of tempered coated glass products is obviously greenish is that the composite nano-film layer it is coated needs to withstand high temperatures for a long time, so sufficient protective layers (such as SiNx layer, NiCr layer) are added to the film material. ) to protect the low-emissivity silver layer. These protective layers selectively transmit green light, causing the color of the common temperable coating products on the market to appear light green, affecting human visual effects.

As aesthetic perspectives continue to change, the market's demand for the transmission color of coated products has also become diversified. Tempered LOW-E coated glass products with neutral transmission colors have strong market demand.

Contents of the invention

The invention provides an ultra-low reflection temperable LOW-E glass, which not only has low reflectivity, but also has neutral transmission color.

In order to achieve the above object, the technical solution adopted by the present invention is: an ultra-low reflection temperable LOW-E glass, including a glass matrix and a composite film layer plated on the surface of the glass matrix, the composite film layer including The glass substrate is coated with a first dielectric layer, a transition layer, a first seed layer, a first functional layer, a first protective layer, a first AZO layer, a second dielectric layer, a second seed layer, and a second function layer facing outward. layer, a second protective layer, a second AZO layer and a third dielectric layer, the first functional layer is a Cu layer, and the second functional layer is an Ag layer.

Further, the thickness of the first functional layer is 9-15 nm; the thickness of the second functional layer is 6-18 nm.

Further, the transition layer is a TiOx layer.

Further, the thickness of the transition layer is 6-12 nm.

Further, the first seed layer and the second seed layer are ZnOx layers.

Further, the thickness of the first seed layer and the second seed layer is 30-45 nm.

Further, the first dielectric layer and the second dielectric layer are SiNx layers, and the third dielectric layer is a SiNx layer, a SiOx layer, a SiNxOy layer or a composite layer of any multiple layers above.

Further, the thickness of the first dielectric layer is 38-55 nm; the thickness of the second dielectric layer is 50-68 nm; and the thickness of the third dielectric layer is 36-50 nm.

Further, the thickness of the first AZO layer and the second AZO layer is 8-10 nm.

Further, the first protective layer and the second protective layer are NiCr layers, the thickness of the first protective layer is 0.8-6nm; the thickness of the second protective layer is 2.1-6nm.

After adopting the above technical solution, the present invention has the following advantages compared with the prior art: by optimizing the thickness of each film layer, the present invention sets the first functional layer as a Cu layer, the transition layer as a TiOx layer, the first seed layer and The second seed layer is set as a ZnOx layer, which can reduce the visible light reflectance of the product. The visible light reflectance of the glass product of the present invention is between 7% and 9%, and setting the first functional layer as a Cu layer can solve the existing problems. The problem of greener transmission color of tempered LOW-E products can also reduce production costs; the present invention provides a TiOx layer as a transition layer between the first dielectric layer (i.e., base layer) and the first seed layer, which can solve the problem of film layer attachment. It solves the problem of poor strength and further protects the functional layer.

Description of drawings

Figure 1 is a schematic structural diagram of the ultra-low reflection temperable LOW-E glass of the present invention.

in,

100. Glass matrix;

200. Composite film layer;

1. First dielectric layer; 2. Transition layer; 3. First seed layer; 4. First functional layer; 5. First protective layer; 6. First AZO layer; 7. Second dielectric layer; 8. Two sub-layers; 9. Second functional layer; 10. Second protective layer; 11. Second AZO layer; 12. Third dielectric layer.

Detailed ways

The present invention will be further described below in conjunction with the accompanying drawings and examples.

As shown in Figure 1, an ultra-low reflection temperable LOW-E glass includes a glass substrate 100 and a composite film layer 200 plated on the surface of the glass substrate 100. The composite film layer 200 includes layers plated sequentially from the glass substrate 100 outward. The first dielectric layer 1, transition layer 2, first seed layer 3, first functional layer 4, first protective layer 5, first AZO layer 6, second dielectric layer 7, second seed layer 8, second functional layer Layer 9, second protective layer 10, second AZO layer 11 and third dielectric layer 12.

specific:

The first functional layer 4 is a Cu layer, and the thickness of the first functional layer 4 is 9-15 nm. The second functional layer 9 is an Ag layer, and the thickness of the second functional layer 9 is 6-18 nm. The present invention uses pure metal copper to replace the traditional functional layer silver as the first functional layer 4. Compared with silver, copper has stronger selective absorption of visible light, resulting in less visible light being reflected; at the same time, due to the selective absorption of copper, it can The transparent color of glass products can be made into a neutral tone, which solves the problem of traditional tempered glass products having a greenish transmitted color. Since the price of copper is lower than that of silver, it can also reduce production costs.

The transition layer 2 is a TiOx layer, and the thickness of the transition layer 2 is 6-12 nm. The TiOx layer of the present invention has a three-dimensional network structure composed of nano-sized TiOx particles connected to each other. It can be firmly combined with the first dielectric layer 1 and the seed layer to increase the adhesion of the film layer and effectively solve the traditional toughening problem. The film layer of glass products has poor adhesion and is easy to peel off. In addition, TiOx has a high refractive index. Through the principle of light interference, it can increase the overall light transmittance of the film layer and reduce the reflectivity of the glass surface.

The first seed layer 3 and the second seed layer 8 are ZnOx layers, and the thicknesses of the first seed layer 3 and the second seed layer 8 are both 30-45 nm. In the present invention, setting the first seed layer 3 and the second seed layer 8 as ZnOx layers can improve the flatness of the film layer and provide a better growth platform for the functional layer. If the functional layer is deposited on other dielectric film materials, the The quality of the functional layers obtained will be poor, resulting in reduced performance of the glass product. At the same time, due to the low extinction coefficient K value of ZnOx, infiltrating ZnOx into the dielectric layer can relatively increase the transmittance of the entire composite film layer 200 and reduce the visible light reflectance.

The first dielectric layer 1 and the second dielectric layer 7 are SiNx layers, and the third dielectric layer 12 is a SiNx layer, a SiOx layer, a SiNxOy layer, or a composite layer of any of the above layers. The thickness of the first dielectric layer 1 is 38-55 nm; the thickness of the second dielectric layer 7 is 50-68 nm; and the thickness of the third dielectric layer 12 is 36-50 nm. The film materials of the first dielectric layer 1, the second dielectric layer 7 and the third dielectric layer 12 of the present invention have excellent physical properties and chemical corrosion resistance, and the plated film layers have strong corrosion resistance and mechanical resistance. Scratch and high temperature resistance, thereby improving the subsequent processing performance and service life of the product.

In addition, since the SiNx layer has a columnar amorphous structure and the ZnOx layer has a columnar crystal structure, the binding force between the two is very poor. The TiOx layer is a three-dimensional network structure composed of nano-sized TiOx particles connected to each other, and the structure is stable. It can protect the functional layer during the tempering process and combines well with the SiNx layer and ZnOx layer. Therefore, the TiOx layer is selected as the transition layer 2 between the first dielectric layer 1 and the first seed layer 3 to increase the adhesion of the film layer. It has effectively solved the problems of poor film adhesion and easy decoating of traditional temperable products; and the TiOx layer has a high refractive index, which can improve the overall light transmittance of the film and reduce the reflectivity of visible light; at the same time, due to During the tempering process, the ability of the first dielectric layer 1 and the first seed layer 3 to block oxygen atoms from entering the functional layer is weak, and TiOx can block oxygen atoms to prevent the functional layer from being more closely combined with the atoms in the upper and lower layers. Oxidation.

The thickness of the first AZO layer 6 and the second AZO layer 11 is 8-10 nm. The first protective layer 5 and the second protective layer 10 are NiCr layers. The thickness of the first protective layer 5 is 0.8-6 nm; the thickness of the second protective layer 10 is 2.1-6 nm.

Each film layer in the composite film layer 200 is sequentially coated on the glass substrate 100 using a magnetron sputtering coating method, and the coated glass obtained above is tempered. The specific steps are as follows: Place the coated glass in a tempering furnace, and coat The heating temperature of the surface is 670-700°C. Since the composite film layer 200 is a low-emissivity film layer, its performance determines that the heat absorption capacity of the composite film layer 200 is not as strong as that of the non-coated surface. In order to ensure that the heat absorption of the coated surface and the non-coated surface is consistent To prevent the coated glass from being bent during the tempering process, the temperature of the coated surface needs to be higher than that of the non-coated surface. The heating temperature of the non-coated surface of the glass substrate 100 is 670-680°C.

The following are specific examples.

Example 1

The structure of the composite film layer 200 of the ultra-low reflection temperable LOW-E glass temperable double silver low-e coated glass is: SiNx layer/TiOx layer/ZnOx layer/Cu layer/NiCr layer/AZO layer/SiNx layer/ZnOx layer /Ag layer/NiCr layer/AZO layer/SiNx layer;

The thickness of each of the above film layers is:

41nm/6.8nm/43nm/9.8nm/2nm/8.2nm/62.3nm/31.8nm/12.2nm/3nm/9.5nm/39.4nm.

The preparation method of the above glass products is:

(1) Using a magnetron sputtering process, the first dielectric layer 1 is plated on the glass substrate 100: under the control of an intermediate frequency AC power supply, the silicon target is placed in a mixed atmosphere of argon and nitrogen (Ar:N ₂ =9:7) Sputtering deposition is used to deposit the first dielectric layer 1 with a film thickness of 41 nm, and the first dielectric layer 1 is a SiNx layer.

(2) Using the magnetron sputtering process, the transition layer 2 is plated on the first dielectric layer 1: Under the control of the intermediate frequency AC power supply, the TiOx target is sputtered and deposited in a pure argon atmosphere, and the thickness of the deposited film layer is 6.8nm. Layer 2, transition layer 2 is the TiOx layer.

(3) Using a magnetron sputtering process, the first seed layer 3 is plated on the transition layer 2: Under the control of a medium-frequency AC power supply, the ZnAl target is placed in a mixed atmosphere of argon and oxygen (Ar:O ₂ =7:10) Sputtering deposition is used to deposit the first seed layer 3 with a film thickness of 43 nm, and the first seed layer 3 is a ZnOx layer.

(4) Using the magnetron sputtering process, the first functional layer 4 is plated on the first seed layer 3 (ZnOx): Under the control of the DC power supply, the Cu target is sputtered and deposited in a pure argon atmosphere, and the thickness of the deposited film layer is the first functional layer 4 of 9.8 nm, and the first functional layer 4 is a Cu layer.

(5) Using a magnetron sputtering process, the first protective layer 5 is plated on the first functional layer 4: Under the control of a DC power supply, the NiCr target is sputtered and deposited in an argon atmosphere, and the deposited film layer is 2 nm thick. A protective layer 5, the first protective layer 5 is a NiCr layer.

(6) Using a magnetron sputtering process, the first AZO layer 6 is plated on the first protective layer 5: Under the control of a medium-frequency AC power supply, the AZO target is sputtered and deposited in an argon atmosphere, and the thickness of the deposited film is 8.2nm. The first AZO layer 6.

(7) Use a magnetron sputtering process to plate the second dielectric layer 7 on the first AZO layer 6: Under the control of an intermediate frequency AC power supply, the silicon target is placed in a mixed atmosphere of argon and nitrogen (Ar:N ₂ =9:7 ), deposit a second dielectric layer 7 with a film thickness of 62.3 nm, and the second dielectric layer 7 is a SiNx layer.

(8) Use the magnetron sputtering process to plate the second seed layer 8 on the second dielectric layer 7: Under the control of the intermediate frequency AC power supply, the Zn target is placed in a mixed atmosphere of argon and oxygen (Ar:O ₂ =7:10 ), deposit a second seed layer 8 with a film thickness of 31.8 nm, and the second seed layer 8 is a ZnOx layer.

(9) Using the magnetron sputtering process, the second functional layer 9 is plated on the second seed layer 8 (ZnOx): Under the control of the DC power supply, the Ag target is sputtered and deposited in a pure argon atmosphere, and the thickness of the deposited film is is the second functional layer 9 of 12.2 nm, and the second functional layer 9 is an Ag layer.

(10) Using a magnetron sputtering process, the second protective layer 10 is plated on the second functional layer 9: Under the control of a DC power supply, the NiCr target is sputtered and deposited in an argon atmosphere, and the deposited film layer is 3 nm thick. The second protective layer 10 is a NiCr layer.

(11) Using a magnetron sputtering process, the second AZO layer 11 is plated on the second protective layer 10: under the control of a medium-frequency AC power supply, the AZO target is sputtered and deposited in an argon atmosphere, and the thickness of the deposited film is 9.5nm. The second AZO layer 11.

(12) Using a magnetron sputtering process, the third dielectric layer 12 is plated on the second AZO layer 11: under the control of an intermediate frequency AC power supply, the silicon target is placed in a mixed atmosphere of argon and nitrogen (Ar:N ₂ =9:7) Next, sputtering is performed to deposit a third dielectric layer 12 with a film thickness of 39.4 nm, and the third dielectric layer 12 is a SiNx layer.

The coated glass prepared above is tempered, and the heating temperature of the coated surface is 670-700°C, and the heating temperature of the non-coated surface of the glass substrate 100 is 670-680°C.

The colors of the glass products produced above before and after tempering are shown in Table 1.

Table 1

The optical performance test of the glass product obtained in Example 1 is as follows:

Before tempering, the emissivity of a single piece of low-emissivity coated glass is 0.065, the glass surface reflectance is 5.33%, and the visible light transmittance is 53.8%; after tempering, the emissivity of a single piece of low-emissivity coated glass is 0.071, and the glass surface reflectance is 8.37%, the visible light transmittance is 60.6%; after tempering, a*t=-0.23, b*t=0.76. It can be seen that the reflectivity after tempering is low, there is basically no light pollution, and the transmitted color is also very good. neutral.

In accordance with GB9656-2003, the film of the tempered glass product was wiped and it was found that the film did not peel off; the impact test, radiation resistance test, and heat and humidity cycle test of the tempered glass product all met the requirements. After testing, the knocking test level is level 4.

Example 2

The structure of the composite film layer 200 of the ultra-low reflection temperable LOW-E glass temperable double silver low-e coated glass is: SiNx layer/TiOx layer/ZnOx layer/Cu layer/NiCr layer/AZO layer/SiNx layer/ZnOx layer /Ag layer/NiCr layer/AZO layer/SiNxOy layer;

The thickness of each of the above film layers is:

53nm/10.9nm/43nm/14.3nm/4.3nm/8.6nm/55.3nm/31.8nm/17.3nm/4.1nm/9.3nm/41.9nm.

The thickness of each of the above film layers is:

(1) Using a magnetron sputtering process, the first dielectric layer 1 is plated on the glass substrate 100: under the control of an intermediate frequency AC power supply, the silicon target is placed in a mixed atmosphere of argon and nitrogen (Ar:N ₂ =9:7) Sputtering deposition is used to deposit the first dielectric layer 1 with a film thickness of 53 nm, and the first dielectric layer 1 is a SiNx layer.

(2) Using the magnetron sputtering process, the transition layer 2 is plated on the first dielectric layer 1: Under the control of the intermediate frequency AC power supply, the TiOx target is sputtered and deposited in a pure argon atmosphere, and the thickness of the deposited film layer is 10.9nm. Layer 2, transition layer 2 is the TiOx layer.

(3) Using a magnetron sputtering process, the first seed layer 3 is plated on the transition layer 2TiOx: under the control of a medium-frequency AC power supply, the ZnAl target is placed in a mixed atmosphere of argon and oxygen (Ar:O ₂ =7:10) Sputtering deposition is used to deposit the first seed layer 3 with a film thickness of 43 nm, and the first seed layer 3 is a ZnOx layer.

(4) Using the magnetron sputtering process, the first functional layer 4 is plated on the first seed layer 3: Under the control of the DC power supply, the Cu target is sputtered and deposited in a pure argon atmosphere, and the thickness of the deposited film is 14.3nm. The first functional layer 4 is a Cu layer.

(5) Using the magnetron sputtering process, the first protective layer 5 is plated on the first functional layer 4: Under the control of the DC power supply, the NiCr target is sputtered and deposited in an argon atmosphere, and the deposited film layer thickness is 4.3nm. The first protective layer 5 is a NiCr layer.

(6) Using a magnetron sputtering process, the first AZO layer 6 is plated on the first protective layer 5: Under the control of a medium-frequency AC power supply, the AZO target is sputtered and deposited in an argon atmosphere, and the thickness of the deposited film is 8.6nm. The first AZO layer 6.

(7) Use a magnetron sputtering process to plate the second dielectric layer 7 on the first AZO layer 6: Under the control of an intermediate frequency AC power supply, the silicon target is placed in a mixed atmosphere of argon and nitrogen (Ar:N ₂ =9:7 ), deposit a second dielectric layer 7 with a film thickness of 55.3 nm, and the second dielectric layer 7 is a SiNx layer.

(8) Use the magnetron sputtering process to plate the second seed layer 8 on the second dielectric layer 7: Under the control of the intermediate frequency AC power supply, the Zn target is placed in a mixed atmosphere of argon and oxygen (Ar:O ₂ =7:10 ), deposit a second seed layer 8 with a film thickness of 31.8 nm, and the second seed layer 8 is a ZnOx layer.

(9) Using a magnetron sputtering process, the second functional layer 9 is plated on the second seed layer 8: Under the control of a DC power supply, the Ag target is sputtered and deposited in a pure argon atmosphere, and the thickness of the deposited film is 17.3nm. The second functional layer 9 is an Ag layer.

(10) Using a magnetron sputtering process, the second protective layer 10 is plated on the second functional layer 9: Under the control of a DC power supply, the NiCr target is sputtered and deposited in an argon atmosphere, and the deposited film layer thickness is 4.1nm. The second protective layer 10 is a NiCr layer.

(11) Using a magnetron sputtering process, the second AZO layer 11 is plated on the second protective layer 10: under the control of a medium-frequency AC power supply, the AZO target is sputtered and deposited in an argon atmosphere, and the thickness of the deposited film is 9.3nm. The second AZO layer 11.

(12) Using a magnetron sputtering process, the third dielectric layer 12 is plated on the second AZO layer 11: under the control of a medium-frequency AC power supply, the silicon target is placed in a mixed atmosphere of argon and nitrogen (Ar:N ₂ :O ₂ = 9:6:1), the third dielectric layer 12 with a film thickness of 41.9 nm is deposited, and the third dielectric layer 12 is a SiNxOy layer.

The coated glass prepared above is tempered, and the heating temperature of the coated surface is 670-700°C, and the heating temperature of the non-coated surface of the glass substrate 100 is 670-680°C.

The colors of the glass products produced above before and after tempering are shown in Table 2.

Table 2

The optical performance test of the glass product obtained in Example 2 is as follows:

Before tempering, the emissivity of a single piece of low-emissivity coated glass is 0.059, the glass surface reflectance is 5.33%, and the visible light transmittance is 48.6%; after tempering, the emissivity of a single piece of low-emissivity coated glass is 0.063, and the glass surface reflectance is 0.063. 7.62%, the visible light transmittance is 53.2%; after tempering, a*t=0.76, b*t=-0.97. It can be seen that the reflectivity after tempering is low, there is basically no light pollution, and the transmitted color is also very good. neutral.

In accordance with GB9656-2003, the film of the tempered glass product was wiped and it was found that the film did not peel off; the impact test, radiation resistance test, and heat and humidity cycle test of the tempered glass product all met the requirements. After testing, the knocking test level is level 4.

The above embodiments are only for illustrating the technical concepts and characteristics of the present invention. Their purpose is to enable those familiar with this technology to understand the content of the present invention and implement it accordingly. They cannot limit the scope of protection of the present invention. All equivalent changes or modifications made based on the spirit and essence of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. An ultra-low reflection temperable LOW-E glass, including a glass matrix and a composite film layer plated on the surface of the glass matrix, and is characterized by: The composite film layer includes a first dielectric layer, a transition layer, a first seed layer, a first functional layer, a first protective layer, a first AZO layer, and a second dielectric layer that are sequentially plated outward from the glass substrate. a second seed layer, a second functional layer, a second protective layer, a second AZO layer and a third dielectric layer, where the first functional layer is a Cu layer and the second functional layer is an Ag layer; The thickness of the first functional layer is 9-15nm; the thickness of the second functional layer is 6-18nm; The transition layer is a TiOx layer; The first seed layer and the second seed layer are ZnOx layers. 2. An ultra-low reflection temperable LOW-E glass according to claim 1, characterized in that: The thickness of the transition layer is 6-12nm. 3. An ultra-low reflection temperable LOW-E glass according to claim 1, characterized in that: The thickness of the first seed layer and the second seed layer is 30-45 nm. 4. An ultra-low reflection temperable LOW-E glass according to claim 1, characterized in that: The first dielectric layer and the second dielectric layer are SiNx layers, and the third dielectric layer is a SiNx layer, a SiOx layer, a SiNxOy layer, or a composite layer of any of the above layers. 5. An ultra-low reflection temperable LOW-E glass according to claim 4, characterized in that: The thickness of the first dielectric layer is 38-55 nm; the thickness of the second dielectric layer is 50-68 nm; and the thickness of the third dielectric layer is 36-50 nm. 6. An ultra-low reflection temperable LOW-E glass according to claim 1, characterized in that: The thickness of the first AZO layer and the second AZO layer is 8-10 nm. 7. An ultra-low reflection temperable LOW-E glass according to claim 1, characterized in that: The first protective layer and the second protective layer are NiCr layers. The thickness of the first protective layer is 0.8-6nm; the thickness of the second protective layer is 2.1-6nm.