CN116874199A

CN116874199A - Low-emissivity coated glass and preparation method thereof

Info

Publication number: CN116874199A
Application number: CN202311152496.XA
Authority: CN
Inventors: 刘静静; 窦雪; 薛鹏; 肇启文; 窦帅; 郑学臻; 窦杰; 马连群
Original assignee: Shandong Blue Glass Technology Co ltd
Current assignee: Shandong Blue Glass Technology Co ltd
Priority date: 2023-09-08
Filing date: 2023-09-08
Publication date: 2023-10-13
Anticipated expiration: 2043-09-08
Also published as: CN116874199B

Abstract

The invention provides low-emissivity coated glass and a preparation method thereof, and belongs to the field of coated glass. The preparation method of the low-emissivity coated glass comprises the following steps of: primary treatment, secondary treatment, film plating and post treatment. The low-emissivity coated glass and the preparation method thereof can synchronously improve the visible light transmission performance, the visible light reflection performance, the far infrared light transmission performance and the far infrared light reflection performance of the low-emissivity coated glass while reducing the heat transfer coefficient of the low-emissivity coated glass; the film thickness of the low-emissivity coated glass is uniform, the compatibility between the film and the glass substrate and between the film layers is good, and the firmness of the film layers is good; further improving the stability and weather resistance of the low-emissivity coated glass.

Description

Low-emissivity coated glass and preparation method thereof

Technical Field

The invention relates to the field of coated glass, in particular to low-emissivity coated glass and a preparation method thereof.

Background

Coated glass is also known as reflective glass. The coated glass is prepared by coating one or more layers of metal, alloy or metal compound films on the surface of the glass so as to change the optical performance of the glass and meet the specific application requirements. The coated glass can be mainly divided into: low emissivity coated glass (Low-E), thermally reflective coated glass, electrically conductive coated glass, and the like.

The Low-emissivity coated glass, also called as Low-E coated glass, refers to special glass with Low emissivity by coating a plurality of metal or other compound film layers with Low surface emissivity on the surface of the glass. The Low-E coated glass is a green, energy-saving and environment-friendly glass product. The surface emissivity of the existing common glass is about 0.84, and the surface emissivity of the low-emissivity coated glass can reach below 0.25.

The low-emissivity coated glass has a low-emissivity coating layer with a thickness less than one percent of the thickness of hair, has high reflectivity to far infrared heat radiation, and can reflect most of the far infrared heat radiation back, thereby realizing the heat insulation effect. Compared with common transparent float glass and heat absorption glass, the far infrared reflectivity of the glass is only about 12%, and the low-radiation coated glass has good heat-insulating radiation permeation resistance and heat insulation effects. Meanwhile, the low-emissivity coated glass generally has a lower heat transfer coefficient, and can reflect external far infrared heat radiation and simultaneously prevent internal heat from being dissipated, so that the heat preservation effect of the low-emissivity coated glass is realized.

When in winter, the low-radiation coated glass can reflect most of heat radiation back to the room like a heat reflecting mirror, and meanwhile, the low-radiation coated glass has good low heat transfer performance, so that the indoor heat is ensured not to be dissipated to the outside, and the heating cost is further saved. In summer, the low-radiation coated glass can prevent heat radiation emitted by outdoor sun, ground, buildings and the like from entering the room, and meanwhile, the low-radiation coated glass is combined with good heat transfer performance, so that the refrigerating cost of an air conditioner is saved. In addition, the visible light reflectivity of the low-emissivity coated glass is generally below 15 percent, which is similar to that of common white glass, and the light pollution caused by light reflection can be effectively avoided.

According to the manufacturing process of the low-emissivity coated glass, the low-emissivity coated glass can be divided into on-line low-emissivity coated glass and off-line low-emissivity coated glass, and the low-emissivity coated glass in the prior art is prepared by sequentially coating a plurality of functional film layers comprising a single silver layer or double silver layers on a glass substrate by adopting a magnetron sputtering coating technology.

However, the visible light transmittance, visible light reflectance, far infrared light transmittance and far infrared light reflectance of the existing low-emissivity coated glass have contradictory relation with the heat transfer coefficient of the low-emissivity coated glass, so that the visible light transmittance, visible light reflectance, far infrared light transmittance and far infrared light reflectance of the low-emissivity coated glass cannot be synchronously improved while the heat transfer coefficient of the low-emissivity coated glass is reduced.

Further, the inventor finds that the low-emissivity coated glass with a double-silver-layer structure has the problem of uneven thickness of a film layer in the preparation process; and the compatibility between the film layers and the glass substrate and between the film layers is not ideal, the firmness of the film layers is not good, and the problems of demolding or film layer damage and the like exist in the subsequent processing, storage, transportation, erection and application processes of the low-emissivity coated glass. Meanwhile, the stability and weather resistance of the low-emissivity coated glass are still to be further improved.

Disclosure of Invention

In order to solve the technical problems in the prior art, the invention provides the low-emissivity coated glass and the preparation method thereof, which can synchronously improve the visible light transmission performance, the visible light reflection performance, the far infrared light transmission performance and the far infrared light reflection performance of the low-emissivity coated glass while reducing the heat transfer coefficient of the low-emissivity coated glass; the film thickness of the low-emissivity coated glass is uniform, the compatibility between the film and the glass substrate and between the film layers is good, and the firmness of the film layers is good; and the stability and weather resistance of the low-emissivity coated glass are further improved.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

a low-emissivity coated glass and a preparation method thereof are provided, wherein the low-emissivity coated glass comprises the following steps: primary treatment, secondary treatment, film plating and post treatment.

The one-time treatment method comprises the steps of cleaning a glass substrate with deionized water for 2-3 times, and drying with an air knife at 30-35 ℃ to obtain a clean glass substrate; then placing the clean glass substrate in a closed treatment bin, and uniformly spraying primary treatment liquid with the temperature of 35-45 ℃ to the clean glass substrate; after the primary treatment liquid is sprayed, the temperature of the treatment bin is controlled to be increased to 150-160 ℃ at the heating rate of 2-3 ℃/min, the temperature is kept for 15-30min, the glass substrate is naturally cooled to normal temperature, and the glass substrate is taken out and cleaned by deionized water and dried, so that the primary treatment substrate is obtained.

In the primary treatment, the primary treatment liquid is deionized water solution of a silane coupling agent KH-550; in the primary treatment liquid, the concentration of the silane coupling agent KH-550 is 0.7-0.8wt%;

the volume ratio of the primary treatment liquid to the clean glass substrate is 3-5:1.

The secondary treatment method comprises the steps of carrying out plasma treatment on a primary treatment substrate in an argon atmosphere environment, controlling the discharge voltage of the plasma to be 12-13KV and the discharge frequency to be 28-30KHz; controlling the distance between the primary treatment substrate and the spray head of the plasma treatment equipment to be 8-10mm, and controlling the advancing speed of the primary treatment substrate relative to the spray head of the plasma treatment equipment to be 0.1-0.15m/s; and finishing the secondary treatment to obtain a secondary treatment substrate.

The film plating method comprises the steps of plating a TiN layer, a first NiCr layer, a first Ag layer, a second NiCr layer, a first ZnAlO layer, a SiAl layer, a third NiCr layer, a second Ag layer, a fourth NiCr layer, a second ZnAlO layer and a SiN layer on the surface of a secondary treatment substrate in sequence to obtain a coated glass substrate.

Further, the method for plating the TiN layer comprises the steps of sputtering a titanium target material by adopting an alternating-current medium-frequency power supply and taking argon as sputtering gas and nitrogen as reaction gas through a magnetron sputtering coating process, and plating the TiN layer on the surface of the secondary treatment substrate; controlling the thickness of the TiN layer to be 50-60nm to obtain a glass substrate plated with the TiN layer;

In the TiN coating, the flow ratio of argon to nitrogen is controlled to be 500-550SCCM to 650-700SCCM.

The method for plating the first NiCr layer comprises the steps of sputtering a nickel-chromium alloy target material by using a direct current power supply and taking argon as sputtering gas through a magnetron sputtering coating process, and plating the first NiCr layer on the surface of the glass substrate plated with the TiN layer; controlling the thickness of the first NiCr layer to be 2-3nm to obtain a glass substrate plated with the first NiCr layer;

and (3) plating a first NiCr layer, wherein the flow rate of argon is controlled to be 500-600SCCM.

The method for plating the first Ag layer comprises the steps of sputtering a silver target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and plating the first Ag layer on the surface of the glass substrate plated with the first NiCr layer; controlling the thickness of the first Ag layer to be 8-10nm to obtain a glass substrate plated with the first Ag layer;

and in the first Ag layer plating, controlling the flow of argon to be 500-600SCCM.

The method for plating the second NiCr layer comprises the steps of sputtering a nickel-chromium alloy target material by using a direct current power supply and taking argon as sputtering gas through a magnetron sputtering coating process, and plating the second NiCr layer on the surface of the glass substrate plated with the first Ag layer; controlling the thickness of the second NiCr layer to be 2-3nm to obtain a glass substrate plated with the second NiCr layer;

And (3) plating a second NiCr layer, wherein the flow rate of argon is controlled to be 500-600SCCM.

The method for plating the first ZnAlO layer comprises the steps of sputtering a zinc-aluminum alloy target material by using an alternating-current intermediate-frequency power supply and using argon as sputtering gas and oxygen as reaction gas through a magnetron sputtering coating process, and plating the first ZnAlO layer on the surface of the glass substrate plated with the second NiCr layer; controlling the thickness of the first ZnAlO layer to be 13-16nm, and obtaining a glass substrate plated with the first ZnAlO layer;

in the first ZnAlO layer, the flow ratio of argon to oxygen is controlled to be 700-750SCCM to 100-120SCCM.

The SiAl layer plating method comprises the steps of sputtering an aluminum-silicon alloy target material (Si content is 30-32 wt%) by using an alternating-current medium-frequency power supply and argon as sputtering gas and nitrogen as reaction gas through a magnetron sputtering coating process, and plating the SiAl layer on the surface of the glass substrate plated with the first ZnAlO layer; controlling the thickness of the SiAl layer to be 55-65nm to obtain a glass substrate plated with the SiAl layer;

in the SiAl layer plating, the flow ratio of argon to nitrogen is controlled to be 500-550SCCM to 600-650SCCM.

The third NiCr layer is plated on the surface of the glass substrate plated with the SiAl layer by a magnetron sputtering coating process by adopting a direct current power supply and taking argon as sputtering gas to sputter a nickel-chromium alloy target; controlling the thickness of the third NiCr layer to be 2-3nm to obtain a glass substrate plated with the third NiCr layer;

And in the third NiCr layer plating, controlling the flow of argon to be 500-600SCCM.

The method for plating the second Ag layer comprises the steps of sputtering a silver target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and plating the second Ag layer on the surface of the glass substrate plated with the third NiCr layer; controlling the thickness of the second Ag layer to be 8-10nm to obtain a glass substrate plated with the second Ag layer;

and in the second Ag layer plating, controlling the flow of argon to be 500-600SCCM.

The method for plating the fourth NiCr layer comprises the steps of sputtering a nickel-chromium alloy target material by using a direct current power supply and taking argon as sputtering gas through a magnetron sputtering coating process, and plating the fourth NiCr layer on the surface of the glass substrate plated with the second Ag layer; controlling the thickness of the fourth NiCr layer to be 2-3nm to obtain a glass substrate plated with the fourth NiCr layer;

and in the fourth NiCr layer, controlling the flow of argon to be 500-600SCCM.

The second ZnAlO layer is plated on the surface of the glass substrate plated with the fourth NiCr layer by a magnetron sputtering coating process by adopting an alternating-current intermediate-frequency power supply, taking argon as sputtering gas and oxygen as reaction gas to sputter a zinc-aluminum alloy target; controlling the thickness of the second ZnAlO layer to be 13-16nm, and obtaining a glass substrate plated with the second ZnAlO layer;

In the second ZnAlO layer, the flow ratio of argon to oxygen is controlled to be 700-750SCCM to 100-120SCCM.

The SiN layer plating method comprises the steps of sputtering a silicon target material by using an alternating-current medium-frequency power supply and using argon as sputtering gas and nitrogen as reaction gas through a magnetron sputtering coating process, and plating the SiN layer on the surface of the glass substrate plated with the second ZnAlO layer; and controlling the thickness of the SiN layer to be 40-50nm to obtain a coated glass substrate;

in the SiN coating, the flow ratio of argon to nitrogen is controlled to be 500-550SCCM to 650-700SCCM.

The post-treatment method comprises the steps of placing a coated glass substrate in a scraper coating device, controlling the scraping thickness of a scraper to be 300-350 mu m, uniformly scraping the coating agent on the surface of the coated glass substrate, placing the coated glass substrate in an environment with the temperature of 20-25 ℃ and the relative humidity of 35-40%, standing for 120-130h, and drying to obtain the low-emissivity coated glass.

In the post-treatment, the coating agent is prepared by the following method: adding polymethyl methacrylate powder, titanate coupling agent 201, 1, 2-diaminocyclohexane and modified polyether silicone oil into tetrahydrofuran, stirring until the components are completely dissolved, heating to 55-60 ℃, keeping the temperature, refluxing and stirring for 1-1.5h, continuously adding nano silicon dioxide and nano titanium dioxide, uniformly dispersing by ultrasonic waves, keeping the temperature, refluxing and stirring for 1-1.5h at 55-60 ℃ to obtain a mixed solution; and uniformly mixing the mixed solution and deionized water according to the weight ratio of 10-11:1, heating to 40-50 ℃, and carrying out heat preservation and stirring for 2-3 hours to obtain the coating agent.

In the preparation of the coating agent, the weight ratio of polymethyl methacrylate powder to titanate coupling agent 201 to 1, 2-diaminocyclohexane to modified polyether silicone oil to nano silicon dioxide to nano titanium dioxide to tetrahydrofuran is 30-32:0.9-1.1:6-7:5-6:3-3.2:1.5-2:250-270.

In the preparation of the coating agent, the modified polyether silicone oil is prepared by the following method: uniformly mixing polyether silicone oil and ethanol solution (volume concentration is 80-85%), heating to 45-55 ℃, and preserving heat; under the stirring condition, simultaneously dripping a silane coupling agent KH-580 and a silane coupling agent KH-590 at the dripping rate of 0.1-0.15mL/min, and continuously preserving heat and stirring for 1-2h after the dripping is completed, and evaporating ethanol in vacuum to obtain the modified polyether silicone oil.

In the preparation of the coating agent, the volume ratio of the polyether silicone oil to the ethanol solution is 1:0.5-0.6;

the weight ratio of the silane coupling agent KH-580 to the silane coupling agent KH-590 to the polyether silicone oil is 2-3:1-2:45-50.

The low-emissivity coated glass is prepared by the preparation method.

Compared with the prior art, the invention has the beneficial effects that:

(1) According to the preparation method of the low-emissivity coated glass, in one treatment, the clean glass substrate is sprayed and subjected to hydrothermal treatment by adopting one-time treatment liquid; in the secondary treatment, plasma treatment is performed on the primary-treated substrate; in film plating, combining film layers with specific sequence and thickness; in the post-treatment, the coating agent is adopted to treat the coated glass substrate, so that the heat transfer coefficient of the low-radiation coated glass can be reduced, and the visible light transmission performance, the visible light reflection performance, the far infrared light transmission performance and the far infrared light reflection performance of the low-radiation coated glass can be synchronously improved; the film thickness of the low-emissivity coated glass is uniform, the compatibility between the film and the glass substrate and between the film layers is good, and the firmness of the film layers is good; and the stability and weather resistance of the low-emissivity coated glass are further improved.

(2) The low-emissivity coated glass has the visible light transmittance of 82.8-83.9%, the visible light reflectance of 5.7-6.0%, the far infrared light transmittance of 33.1-33.7%, the far infrared light reflectance of 48.6-49.2% and the heat transfer coefficient U at night in winter of 1.58-1.61W/(m) ² K) the heat transfer coefficient U in summer and daytime is 1.59-1.62W/(m) ² K), sun shading coefficient SC is 0.40-0.42, solar heat gain coefficient SHGC is 0.35-0.37, and emissivity is 0.04-0.05%.

(3) Through detection, the deviation rate of the thickness of the film layer of the low-emissivity coated glass and the thickness of the process control film layer is 0.38-0.42%, the thickness of the film layer is uniform, the compatibility between the film layers is good, and the film layers are firmly combined.

(4) Through detection, the low-emissivity coated glass has visible light transmittance of 82.1-83.1%, far infrared light reflectivity of 48.1-48.7% and winter heat transfer coefficient U of 1.62-1.66W/(m) after multiple temperature changing processes of-20-60 DEG C ² K) the heat transfer coefficient U in summer and daytime is 1.63-1.67W/(m) ² K) the emissivity is 0.05-0.06%, and the film layer is free from falling off and breakage.

(5) Through detection, the visible light transmittance of the low-emissivity coated glass is 81.1-82.5% after abrasion, and the film layer does not fall off after abrasion; the visible light transmittance after acid treatment is 81.2-82.9%, and the film layer is free from falling off and breakage; the visible light transmittance after alkali treatment is 81.3-82.8%, and the film layer is free from falling off and breakage.

Detailed Description

Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.

Example 1

The embodiment provides a preparation method of low-emissivity coated glass, which specifically comprises the following steps:

1. one-time treatment

Cleaning a glass substrate by deionized water for 2 times, and drying by an air knife at 30 ℃ to obtain a clean glass substrate; then placing the clean glass substrate in a closed treatment bin, and uniformly spraying primary treatment liquid with the temperature of 35 ℃ to the clean glass substrate; after the primary treatment liquid is sprayed, the temperature of the treatment bin is controlled to be raised to 150 ℃ at a heating rate of 2 ℃/min, the temperature is kept for 15min, the glass substrate is naturally cooled to normal temperature, the glass substrate is taken out, and the glass substrate is cleaned by deionized water and dried, so that the primary treatment substrate is obtained.

Wherein the primary treatment liquid is deionized water solution of a silane coupling agent KH-550; in the primary treatment solution, the concentration of the silane coupling agent KH-550 was 0.7wt%.

The volume ratio of the primary treatment liquid to the clean glass substrate is 3:1.

2. Secondary treatment

In an argon atmosphere environment, carrying out plasma treatment on the primary treatment substrate, controlling the plasma discharge voltage to be 12KV and the discharge frequency to be 28KHz; and controlling the distance between the primary treatment substrate and the plasma treatment equipment nozzle to be 8mm, wherein the travelling speed of the primary treatment substrate relative to the plasma treatment equipment nozzle is 0.1m/s; and finishing the secondary treatment to obtain a secondary treatment substrate.

3. Film coating

1) Plating TiN layer

Sputtering a titanium target material by adopting an alternating-current medium-frequency power supply and taking argon as sputtering gas and nitrogen as reaction gas through a magnetron sputtering coating process, and coating a TiN layer on the surface of the secondary treatment substrate; and controlling the thickness of the TiN layer to be 50nm to obtain the glass substrate plated with the TiN layer.

Wherein, the flow ratio of argon to nitrogen is controlled to be 500SCCM to 650SCCM.

2) Plating a first NiCr layer

Sputtering a nichrome target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and coating a first NiCr layer on the surface of the glass substrate coated with the TiN layer; and controlling the thickness of the first NiCr layer to be 2nm to obtain the glass substrate plated with the first NiCr layer.

Wherein, the flow rate of the control argon is 500SCCM.

3) Plating a first Ag layer

Sputtering a silver target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and coating a first Ag layer on the surface of the glass substrate coated with the first NiCr layer; and controlling the thickness of the first Ag layer to be 8nm to obtain the glass substrate plated with the first Ag layer.

Wherein, the flow rate of the control argon is 500SCCM.

4) Plating a second NiCr layer

Sputtering a nichrome target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and plating a second NiCr layer on the surface of the glass substrate plated with the first Ag layer; and controlling the thickness of the second NiCr layer to be 2nm to obtain the glass substrate plated with the second NiCr layer.

Wherein, the flow rate of the control argon is 500SCCM.

5) Plating a first ZnAlO layer

Sputtering a zinc-aluminum alloy target material by using an alternating current intermediate frequency power supply and argon as sputtering gas and oxygen as reaction gas through a magnetron sputtering coating process, and coating a first ZnAlO layer on the surface of the glass substrate coated with the second NiCr layer; and controlling the thickness of the first ZnAlO layer to be 13nm, thereby obtaining the glass substrate plated with the first ZnAlO layer.

Wherein, the flow ratio of the argon to the oxygen is controlled to be 700SCCM to 100SCCM.

6) Plating SiAl layer

Sputtering an aluminum-silicon alloy target material (Si content is 30 wt%) by using an alternating-current medium-frequency power supply and argon as sputtering gas and nitrogen as reaction gas through a magnetron sputtering coating process, and coating a SiAl layer on the surface of the glass substrate coated with the first ZnAlO layer; and controlling the thickness of the SiAl layer to be 55nm, thereby obtaining the glass substrate plated with the SiAl layer.

Wherein, the flow ratio of argon to nitrogen is controlled to be 500SCCM to 600SCCM.

7) Plating a third NiCr layer

Sputtering a nichrome target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and plating a third NiCr layer on the surface of the glass substrate plated with the SiAl layer; and controlling the thickness of the third NiCr layer to be 2nm to obtain the glass substrate plated with the third NiCr layer.

Wherein, the flow rate of the control argon is 500SCCM.

8) Plating a second Ag layer

Sputtering a silver target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and coating a second Ag layer on the surface of the glass substrate coated with the third NiCr layer; and controlling the thickness of the second Ag layer to be 8nm to obtain the glass substrate plated with the second Ag layer.

Wherein, the flow rate of the control argon is 500SCCM.

9) Plating a fourth NiCr layer

Sputtering a nichrome target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and plating a fourth NiCr layer on the surface of the glass substrate plated with the second Ag layer; and controlling the thickness of the fourth NiCr layer to be 2nm to obtain the glass substrate plated with the fourth NiCr layer.

Wherein, the flow rate of the control argon is 500SCCM.

10 Plating a second ZnAlO layer

Sputtering a zinc-aluminum alloy target material by using an alternating current intermediate frequency power supply and argon as sputtering gas and oxygen as reaction gas through a magnetron sputtering coating process, and coating a second ZnAlO layer on the surface of the glass substrate coated with the fourth NiCr layer; and controlling the thickness of the second ZnAlO layer to be 13nm, thereby obtaining the glass substrate plated with the second ZnAlO layer.

11 Plating SiN layer

Sputtering a silicon target material by adopting an alternating current medium-frequency power supply and taking argon as sputtering gas and nitrogen as reaction gas through a magnetron sputtering coating process, and coating a SiN layer on the surface of the glass substrate coated with the second ZnAlO layer; and controlling the thickness of the SiN layer to be 40nm to obtain the coated glass substrate.

4. Post-treatment

And (3) placing the coated glass substrate in a scraper coating device, controlling the scraper to scrape coating thickness to be 300 mu m, uniformly scraping the coating agent on the surface of the coated glass substrate, placing the coated glass substrate in an environment with the temperature of 20 ℃ and the relative humidity of 35%, standing for 120 hours, and drying to obtain the low-emissivity coated glass.

Wherein, the coating agent is prepared by the following method:

adding polymethyl methacrylate powder, titanate coupling agent 201, 1, 2-diaminocyclohexane and modified polyether silicone oil into tetrahydrofuran, stirring until the components are completely dissolved, heating to 55 ℃, keeping the temperature, refluxing and stirring for 1h, continuously adding nano silicon dioxide and nano titanium dioxide, uniformly dispersing by ultrasonic, keeping the temperature, refluxing and stirring for 1h at 55 ℃ to obtain a mixed solution; and uniformly mixing the mixed solution and deionized water according to the weight ratio of 10:1, heating to 40 ℃, and carrying out heat preservation and stirring for 2 hours to obtain the coating agent.

Wherein, the weight ratio of polymethyl methacrylate powder to titanate coupling agent 201 to 1, 2-diaminocyclohexane to modified polyether silicone oil to nano silicon dioxide to nano titanium dioxide to tetrahydrofuran is 30:0.9:6:5:3:1.5:250.

The preparation method of the modified polyether silicone oil comprises the following steps: uniformly mixing polyether silicone oil and ethanol solution (volume concentration is 80%), heating to 45 ℃, and preserving heat; under the stirring condition, simultaneously dripping a silane coupling agent KH-580 and a silane coupling agent KH-590 at the dripping rate of 0.1mL/min, continuously preserving heat and stirring for 1h after the dripping is completed, and evaporating ethanol in vacuum to obtain the modified polyether silicone oil.

Wherein the volume ratio of the polyether silicone oil to the ethanol solution is 1:0.5.

The weight ratio of the silane coupling agent KH-580 to the silane coupling agent KH-590 to the polyether silicone oil is 2:1:45.

The embodiment also provides the low-emissivity coated glass prepared by the preparation method.

Example 2

1. one-time treatment

Cleaning a glass substrate with deionized water for 3 times, and drying by an air knife at 32 ℃ to obtain a clean glass substrate; then placing the clean glass substrate in a closed treatment bin, and uniformly spraying primary treatment liquid with the temperature of 40 ℃ to the clean glass substrate; after the primary treatment liquid is sprayed, the temperature of the treatment bin is controlled to be increased to 155 ℃ at the heating rate of 2.5 ℃/min, the temperature is kept for 25min, the glass substrate is naturally cooled to normal temperature, the glass substrate is taken out, and the glass substrate is cleaned by deionized water and dried, so that the primary treatment substrate is obtained.

Wherein the primary treatment liquid is deionized water solution of a silane coupling agent KH-550; in the primary treatment solution, the concentration of the silane coupling agent KH-550 was 0.75wt%.

The volume ratio of the primary treatment liquid to the clean glass substrate is 4:1.

2. Secondary treatment

In an argon atmosphere environment, carrying out plasma treatment on the primary treatment substrate, controlling the plasma discharge voltage to be 12.5KV and the discharge frequency to be 29KHz; and controlling the distance between the primary treatment substrate and the plasma treatment equipment nozzle to be 9mm, wherein the travelling speed of the primary treatment substrate relative to the plasma treatment equipment nozzle is 0.12m/s; and finishing the secondary treatment to obtain a secondary treatment substrate.

3. Film coating

1) Plating TiN layer

Sputtering a titanium target material by adopting an alternating-current medium-frequency power supply and taking argon as sputtering gas and nitrogen as reaction gas through a magnetron sputtering coating process, and coating a TiN layer on the surface of the secondary treatment substrate; and controlling the thickness of the TiN layer to 55nm to obtain the glass substrate plated with the TiN layer.

Wherein, the flow ratio of the argon to the nitrogen is controlled to be 530SCCM to 680SCCM.

2) Plating a first NiCr layer

Sputtering a nichrome target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and coating a first NiCr layer on the surface of the glass substrate coated with the TiN layer; and controlling the thickness of the first NiCr layer to be 2.5nm, thereby obtaining the glass substrate plated with the first NiCr layer.

Wherein, the flow rate of the control argon is 550SCCM.

3) Plating a first Ag layer

Sputtering a silver target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and coating a first Ag layer on the surface of the glass substrate coated with the first NiCr layer; and controlling the thickness of the first Ag layer to 9nm to obtain the glass substrate plated with the first Ag layer.

Wherein, the flow rate of the control argon is 550SCCM.

4) Plating a second NiCr layer

Sputtering a nichrome target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and plating a second NiCr layer on the surface of the glass substrate plated with the first Ag layer; and controlling the thickness of the second NiCr layer to be 2.5nm, thereby obtaining the glass substrate plated with the second NiCr layer.

Wherein, the flow rate of the control argon is 550SCCM.

5) Plating a first ZnAlO layer

Sputtering a zinc-aluminum alloy target material by using an alternating current intermediate frequency power supply and argon as sputtering gas and oxygen as reaction gas through a magnetron sputtering coating process, and coating a first ZnAlO layer on the surface of the glass substrate coated with the second NiCr layer; and controlling the thickness of the first ZnAlO layer to be 15nm, thereby obtaining the glass substrate plated with the first ZnAlO layer.

Wherein, the flow ratio of argon to oxygen is 720SCCM to 110SCCM.

6) Plating SiAl layer

Sputtering an aluminum-silicon alloy target material (Si content is 31 wt%) by using an alternating-current medium-frequency power supply and argon as sputtering gas and nitrogen as reaction gas through a magnetron sputtering coating process, and coating a SiAl layer on the surface of the glass substrate coated with the first ZnAlO layer; and controlling the thickness of the SiAl layer to be 60nm, thereby obtaining the glass substrate plated with the SiAl layer.

Wherein, the flow ratio of the argon to the nitrogen is controlled to be 520SCCM to 630SCCM.

7) Plating a third NiCr layer

Sputtering a nichrome target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and plating a third NiCr layer on the surface of the glass substrate plated with the SiAl layer; and controlling the thickness of the third NiCr layer to be 2.5nm, thereby obtaining the glass substrate plated with the third NiCr layer.

Wherein, the flow rate of the control argon is 550SCCM.

8) Plating a second Ag layer

Sputtering a silver target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and coating a second Ag layer on the surface of the glass substrate coated with the third NiCr layer; and controlling the thickness of the second Ag layer to be 9nm to obtain the glass substrate plated with the second Ag layer.

Wherein, the flow rate of the control argon is 550SCCM.

9) Plating a fourth NiCr layer

Sputtering a nichrome target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and plating a fourth NiCr layer on the surface of the glass substrate plated with the second Ag layer; and controlling the thickness of the fourth NiCr layer to be 2.5nm, thereby obtaining the glass substrate plated with the fourth NiCr layer.

Wherein, the flow rate of the control argon is 550SCCM.

10 Plating a second ZnAlO layer

Sputtering a zinc-aluminum alloy target material by using an alternating current intermediate frequency power supply and argon as sputtering gas and oxygen as reaction gas through a magnetron sputtering coating process, and coating a second ZnAlO layer on the surface of the glass substrate coated with the fourth NiCr layer; and controlling the thickness of the second ZnAlO layer to be 15nm, thereby obtaining the glass substrate plated with the second ZnAlO layer.

Wherein, the flow ratio of argon to oxygen is controlled to be 730SCCM to 110SCCM.

11 Plating SiN layer

Sputtering a silicon target material by adopting an alternating current medium-frequency power supply and taking argon as sputtering gas and nitrogen as reaction gas through a magnetron sputtering coating process, and coating a SiN layer on the surface of the glass substrate coated with the second ZnAlO layer; and controlling the thickness of the SiN layer to be 45nm to obtain the coated glass substrate.

Wherein, the flow ratio of argon to nitrogen is controlled to be 520SCCM to 680SCCM.

4. Post-treatment

And (3) placing the coated glass substrate in a scraper coating device, controlling the scraper to scrape coating thickness to 320 mu m, uniformly scraping the coating agent on the surface of the coated glass substrate, placing the coated glass substrate in an environment with the temperature of 23 ℃ and the relative humidity of 38%, standing for 125 hours, and drying to obtain the low-emissivity coated glass.

Wherein, the coating agent is prepared by the following method:

adding polymethyl methacrylate powder, titanate coupling agent 201, 1, 2-diaminocyclohexane and modified polyether silicone oil into tetrahydrofuran, stirring until the components are completely dissolved, heating to 58 ℃, keeping the temperature, refluxing and stirring for 1.2 hours, continuously adding nano silicon dioxide and nano titanium dioxide, uniformly dispersing by ultrasonic, and keeping the temperature, refluxing and stirring for 1.2 hours at 58 ℃ to obtain a mixed solution; and uniformly mixing the mixed solution and deionized water according to the weight ratio of 10.5:1, heating to 45 ℃, and carrying out heat preservation and stirring for 2.5h to obtain the coating agent.

Wherein, the weight ratio of polymethyl methacrylate powder to titanate coupling agent 201 to 1, 2-diaminocyclohexane to modified polyether silicone oil to nano silicon dioxide to nano titanium dioxide to tetrahydrofuran is 31:1:6.5:5.5:3.1:1.8:260.

The preparation method of the modified polyether silicone oil comprises the following steps: uniformly mixing polyether silicone oil and ethanol solution (volume concentration is 82%), heating to 50 ℃, and preserving heat; under the stirring condition, simultaneously dripping a silane coupling agent KH-580 and a silane coupling agent KH-590 at the dripping rate of 0.12mL/min, and continuously preserving heat and stirring for 1.5h after the dripping is completed, and evaporating ethanol in vacuum to obtain the modified polyether silicone oil.

Wherein the volume ratio of the polyether silicone oil to the ethanol solution is 1:0.55.

The weight ratio of the silane coupling agent KH-580 to the silane coupling agent KH-590 to the polyether silicone oil is 2.5:1.5:48.

Example 3

1. one-time treatment

Cleaning a glass substrate with deionized water for 3 times, and drying by an air knife at 35 ℃ to obtain a clean glass substrate; then placing the clean glass substrate in a closed treatment bin, and uniformly spraying primary treatment liquid with the temperature of 45 ℃ to the clean glass substrate; after the primary treatment liquid is sprayed, the temperature of the treatment bin is controlled to be raised to 160 ℃ at a heating rate of 3 ℃/min, the temperature is kept for 30min, the glass substrate is naturally cooled to normal temperature, the glass substrate is taken out, and the glass substrate is cleaned by deionized water and dried, so that the primary treatment substrate is obtained.

Wherein the primary treatment liquid is deionized water solution of a silane coupling agent KH-550; in the primary treatment solution, the concentration of the silane coupling agent KH-550 was 0.8wt%.

The volume ratio of the primary treatment liquid to the clean glass substrate is 5:1.

2. Secondary treatment

In an argon atmosphere environment, carrying out plasma treatment on the primary treatment substrate, controlling the plasma discharge voltage to be 13KV and the discharge frequency to be 30KHz; and controlling the distance between the primary treatment substrate and the plasma treatment equipment nozzle to be 10mm, wherein the travelling speed of the primary treatment substrate relative to the plasma treatment equipment nozzle is 0.15m/s; and finishing the secondary treatment to obtain a secondary treatment substrate.

3. Film coating

1) Plating TiN layer

Sputtering a titanium target material by adopting an alternating-current medium-frequency power supply and taking argon as sputtering gas and nitrogen as reaction gas through a magnetron sputtering coating process, and coating a TiN layer on the surface of the secondary treatment substrate; and controlling the thickness of the TiN layer to be 60nm to obtain the glass substrate plated with the TiN layer.

Wherein, the flow ratio of argon to nitrogen is controlled to be 550SCCM to 700SCCM.

2) Plating a first NiCr layer

Sputtering a nichrome target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and coating a first NiCr layer on the surface of the glass substrate coated with the TiN layer; and controlling the thickness of the first NiCr layer to be 3nm to obtain the glass substrate plated with the first NiCr layer.

Wherein, the flow rate of the control argon is 600SCCM.

3) Plating a first Ag layer

Sputtering a silver target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and coating a first Ag layer on the surface of the glass substrate coated with the first NiCr layer; and controlling the thickness of the first Ag layer to be 10nm, thereby obtaining the glass substrate plated with the first Ag layer.

Wherein, the flow rate of the control argon is 600SCCM.

4) Plating a second NiCr layer

Sputtering a nichrome target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and plating a second NiCr layer on the surface of the glass substrate plated with the first Ag layer; and controlling the thickness of the second NiCr layer to be 3nm, thereby obtaining the glass substrate plated with the second NiCr layer.

Wherein, the flow rate of the control argon is 600SCCM.

5) Plating a first ZnAlO layer

Sputtering a zinc-aluminum alloy target material by using an alternating current intermediate frequency power supply and argon as sputtering gas and oxygen as reaction gas through a magnetron sputtering coating process, and coating a first ZnAlO layer on the surface of the glass substrate coated with the second NiCr layer; and controlling the thickness of the first ZnAlO layer to be 16nm, thereby obtaining the glass substrate plated with the first ZnAlO layer.

Wherein, the flow ratio of argon to oxygen is controlled to be 750SCCM to 120SCCM.

6) Plating SiAl layer

Sputtering an aluminum-silicon alloy target material (Si content is 32 wt%) by using an alternating-current medium-frequency power supply and argon as sputtering gas and nitrogen as reaction gas through a magnetron sputtering coating process, and coating a SiAl layer on the surface of the glass substrate coated with the first ZnAlO layer; and controlling the thickness of the SiAl layer to be 65nm, thereby obtaining the glass substrate plated with the SiAl layer.

Wherein, the flow ratio of argon to nitrogen is controlled to be 550SCCM to 650SCCM.

7) Plating a third NiCr layer

Sputtering a nichrome target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and plating a third NiCr layer on the surface of the glass substrate plated with the SiAl layer; and controlling the thickness of the third NiCr layer to be 3nm, thereby obtaining the glass substrate plated with the third NiCr layer.

Wherein, the flow rate of the control argon is 600SCCM.

8) Plating a second Ag layer

Sputtering a silver target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and coating a second Ag layer on the surface of the glass substrate coated with the third NiCr layer; and controlling the thickness of the second Ag layer to be 10nm, thereby obtaining the glass substrate plated with the second Ag layer.

Wherein, the flow rate of the control argon is 600SCCM.

9) Plating a fourth NiCr layer

Sputtering a nichrome target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and plating a fourth NiCr layer on the surface of the glass substrate plated with the second Ag layer; and controlling the thickness of the fourth NiCr layer to be 3nm, thereby obtaining the glass substrate plated with the fourth NiCr layer.

Wherein, the flow rate of the control argon is 600SCCM.

10 Plating a second ZnAlO layer

Sputtering a zinc-aluminum alloy target material by using an alternating current intermediate frequency power supply and argon as sputtering gas and oxygen as reaction gas through a magnetron sputtering coating process, and coating a second ZnAlO layer on the surface of the glass substrate coated with the fourth NiCr layer; and controlling the thickness of the second ZnAlO layer to be 16nm, thereby obtaining the glass substrate plated with the second ZnAlO layer.

11 Plating SiN layer

Sputtering a silicon target material by adopting an alternating current medium-frequency power supply and taking argon as sputtering gas and nitrogen as reaction gas through a magnetron sputtering coating process, and coating a SiN layer on the surface of the glass substrate coated with the second ZnAlO layer; and controlling the thickness of the SiN layer to be 50nm to obtain the coated glass substrate.

4. Post-treatment

And (3) placing the coated glass substrate in a scraper coating device, controlling the scraper to scrape coating thickness to be 350 mu m, uniformly scraping the coating agent on the surface of the coated glass substrate, placing the coated glass substrate in an environment with the temperature of 25 ℃ and the relative humidity of 40%, standing for 130h, and drying to obtain the low-emissivity coated glass.

Wherein, the coating agent is prepared by the following method:

adding polymethyl methacrylate powder, titanate coupling agent 201, 1, 2-diaminocyclohexane and modified polyether silicone oil into tetrahydrofuran, stirring until the components are completely dissolved, heating to 60 ℃, keeping the temperature, refluxing and stirring for 1.5 hours, continuously adding nano silicon dioxide and nano titanium dioxide, uniformly dispersing by ultrasonic, keeping the temperature, refluxing and stirring for 1.5 hours at 60 ℃ to obtain a mixed solution; and uniformly mixing the mixed solution and deionized water according to the weight ratio of 11:1, heating to 50 ℃, and preserving heat and stirring for 3 hours to prepare the coating agent.

Wherein the weight ratio of polymethyl methacrylate powder to titanate coupling agent 201 to 1, 2-diaminocyclohexane to modified polyether silicone oil to nano silicon dioxide to nano titanium dioxide to tetrahydrofuran is 32:1.1:7:6:3.2:2:270.

The preparation method of the modified polyether silicone oil comprises the following steps: uniformly mixing polyether silicone oil and ethanol solution (volume concentration is 85 percent), heating to 55 ℃, and preserving heat; under the stirring condition, simultaneously dripping a silane coupling agent KH-580 and a silane coupling agent KH-590 at the dripping rate of 0.15mL/min, continuously preserving heat and stirring for 2h after the dripping is completed, and evaporating ethanol in vacuum to obtain the modified polyether silicone oil.

Wherein the volume ratio of the polyether silicone oil to the ethanol solution is 1:0.6.

The weight ratio of the silane coupling agent KH-580 to the silane coupling agent KH-590 to the polyether silicone oil is 3:2:50.

Comparative example 1

The technical scheme of the embodiment 2 is adopted, and the difference is that: 1) The primary treatment step is omitted, and the clean glass substrate is directly subjected to secondary treatment. 2) In the film plating step, the first ZnAlO layer and the second ZnAlO layer are omitted.

Comparative example 2

The technical scheme of the embodiment 2 is adopted, and the difference is that: 1) Omitting the secondary treatment step and directly carrying out the film plating step on the primary treatment substrate. 2) And omitting the post-treatment step, and taking the coated glass substrate prepared in the film coating step as a final product.

Comparative example 3

The technical scheme of the embodiment 2 is adopted, and the difference is that: 1) In one treatment, the same volume of deionized water is used to replace the primary treatment liquid. 2) In the preparation of the coating agent for post-treatment, the titanate coupling agent 201, modified polyether silicone oil, nano silicon dioxide and nano titanium dioxide are omitted.

The following properties of the low emissivity coated glasses prepared in examples 1 to 3 and comparative examples 1 to 3 were examined: visible light transmittance, visible light reflectance, far infrared light transmittance, far infrared light reflectance, winter night heat transfer coefficient U, summer day heat transfer coefficient U, sunshade coefficient SC, solar heat gain coefficient SHGC, and emissivity. Meanwhile, an optical interference coating thickness detection device is adopted to randomly select 30 point positions which are uniformly distributed on the low-emissivity coated glass in the embodiment 1-3 and the comparative embodiment 1-3 respectively to detect the thickness of the film, the deviation rate of the thickness of the film detected by each point position and the thickness of the process control film is calculated, the absolute value is taken, and the maximum deviation rate is recorded.

The calculating method of the deviation rate comprises the following steps: [ (Process control film thickness-film thickness detected at a point)/Process control film thickness ]. Times.100%.

The specific results are shown in the following table:

Further, the low-emissivity coated glass of the examples 1-3 and the comparative examples 1-3 is placed in a temperature environment of 60 ℃ and is kept stand for 2 hours; then cooling to-20 ℃ at a cooling rate of 1 ℃/min, and preserving heat and standing for 2 hours; then, the temperature was raised to 60℃at a heating rate of 1℃per minute. And (3) taking out the low-emissivity coated glass after repeating the temperature change process for 1 time and 80 times, naturally rewarming, observing whether the film layer of the low-emissivity coated glass falls off, is damaged or not, and respectively detecting the visible light transmittance, far infrared light reflectivity, winter night heat transfer coefficient U, summer day heat transfer coefficient U and emissivity of each low-emissivity coated glass. The specific results are shown in the following table:

further, the abrasion resistance, acid resistance and alkali resistance of the low emissivity coated glasses of examples 1 to 3 and comparative examples 1 to 3 were examined. Specifically, the method for detecting the wear resistance comprises the steps of respectively placing low-emissivity coated glass on a horizontal rotary table of an abrasion tester, rotating a sample 1000 times, and controlling the width of abrasion marks after abrasion to be not less than 10mm; after abrasion is finished, detecting visible light transmittance of 4 points in an abrasion mark area, and taking an average value; and observing whether the film layer has a falling-off problem.

The method for detecting the acid resistance comprises the steps of respectively immersing the low-emissivity coated glass in hydrochloric acid solution (1 mol/L), heating to 40 ℃, preserving heat and immersing for 24 hours, taking out the low-emissivity coated glass, washing with water, naturally airing, randomly detecting visible light transmittance of 10 points which are uniformly distributed, and taking an average value; and observing whether the film layer is fallen off or damaged.

The alkali resistance detection method comprises the steps of respectively immersing low-emissivity coated glass in sodium hydroxide solution (1 mol/L), heating to 40 ℃, preserving heat and immersing for 24 hours, taking out the low-emissivity coated glass, washing with water, naturally airing, randomly detecting visible light transmittance of 10 points which are uniformly distributed, and taking an average value; and observing whether the film layer is fallen off or damaged.

A detailed detection method for the wear resistance, acid resistance and alkali resistance of low-emissivity coated glass refers to the national standard GB/T18915.2-2013, part 2 of coated glass: the relevant regulations of low emissivity coated glass.

The specific results are shown in the following table:

it can be seen that the preparation method of the low-emissivity coated glass adopts the primary treatment liquid to spray and hydrothermally treat the clean glass substrate in the primary treatment; in the secondary treatment, plasma treatment is performed on the primary-treated substrate; in film plating, combining film layers with specific sequence and thickness; in the post-treatment, the coating agent is adopted to treat the coated glass substrate, so that the heat transfer coefficient of the low-radiation coated glass can be reduced, and the visible light transmission performance, the visible light reflection performance, the far infrared light transmission performance and the far infrared light reflection performance of the low-radiation coated glass can be synchronously improved; the film thickness of the low-emissivity coated glass is uniform, the compatibility between the film and the glass substrate and between the film layers is good, and the firmness of the film layers is good; and the stability and weather resistance of the low-emissivity coated glass are further improved.

As can be seen from comparative example 1, the combination property and compatibility of the film layer and the glass substrate can be effectively improved, the firmness of the film layer is improved, and the stability and weather resistance of the low-emissivity coated glass are further improved by carrying out one-time treatment on the glass substrate and arranging the ZnAlO layer in the composite film layer; meanwhile, the transmission and reflection performance of the low-emissivity coated glass to visible light and far infrared light is improved.

As can be seen from comparative example 2, the present invention can effectively improve the bonding and compatibility of the film layer and the glass substrate and improve the firmness of the film layer by the secondary treatment step and the post-treatment step of the primary treatment substrate; and simultaneously improves the heat transfer and insulation performance and the wear resistance of the low-emissivity coated glass.

As can be seen from comparative example 3, the invention can effectively improve the combination property and compatibility of the film layer and the glass substrate and improve the transmission and reflection properties of the low-radiation coated glass to visible light and far infrared light by adopting the primary treatment liquid in the primary treatment and setting the specific raw material composition in the coating agent of the post-treatment; and simultaneously improves the heat transfer and insulation performance and the wear resistance of the low-emissivity coated glass.

The percentages used in the present invention are mass percentages unless otherwise indicated.

Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The preparation method of the low-emissivity coated glass is characterized by comprising the following steps of: primary treatment, secondary treatment, film plating and post treatment;

the primary treatment method comprises the steps of placing a clean glass substrate in a closed treatment bin, and uniformly spraying primary treatment liquid with the temperature of 35-45 ℃ to the clean glass substrate; after the primary treatment liquid is sprayed, controlling the temperature of a treatment bin to be raised to 150-160 ℃, preserving heat, naturally cooling to normal temperature, taking out the glass substrate, cleaning with deionized water, and drying to obtain a primary treatment substrate;

the primary treatment liquid is deionized water solution of a silane coupling agent KH-550;

The secondary treatment method comprises the steps of performing plasma treatment on a primary treatment substrate in an argon atmosphere environment to obtain a secondary treatment substrate;

the film plating is carried out, and a TiN layer, a first NiCr layer, a first Ag layer, a second NiCr layer, a first ZnAlO layer, a SiAl layer, a third NiCr layer, a second Ag layer, a fourth NiCr layer, a second ZnAlO layer and a SiN layer are sequentially plated on the surface of the secondary treatment substrate through a magnetron sputtering coating process, so that a coated glass substrate is obtained;

the post-treatment is carried out, the coating agent is evenly coated on the surface of a coated glass substrate, then the coated glass substrate is placed in an environment with the temperature of 20-25 ℃ and the relative humidity of 35-40%, and the coated glass substrate is kept stand and dried to obtain the low-emissivity coated glass;

the preparation method of the coating agent comprises the steps of adding polymethyl methacrylate powder, titanate coupling agent 201, 1, 2-diaminocyclohexane and modified polyether silicone oil into tetrahydrofuran, stirring until the polymethyl methacrylate powder, the titanate coupling agent and the modified polyether silicone oil are completely dissolved, stirring and heating to 55-60 ℃, keeping the temperature, refluxing and stirring, continuously adding nano silicon dioxide and nano titanium dioxide, uniformly dispersing by ultrasonic waves, and keeping the temperature, refluxing and stirring at 55-60 ℃ to obtain a mixed solution; and uniformly mixing the mixed solution with deionized water, heating to 40-50 ℃, and carrying out heat preservation and stirring to obtain the coating agent.

2. The method for preparing low-emissivity coated glass according to claim 1, wherein in the one-time treatment, a heating rate of heating to 150-160 ℃ is 2-3 ℃/min, and a holding time is 15-30min;

in the primary treatment liquid, the concentration of the silane coupling agent KH-550 is 0.7-0.8wt%;

3. The method for producing a low-emissivity coated glass according to claim 1, wherein in the secondary treatment, the plasma discharge voltage is controlled to be 12-13KV, and the discharge frequency is controlled to be 28-30KHz;

the distance between the primary treatment substrate and the plasma treatment equipment nozzle is controlled to be 8-10mm, and the travelling speed of the primary treatment substrate relative to the plasma treatment equipment nozzle is controlled to be 0.1-0.15m/s.

4. The method for preparing the low-emissivity coated glass according to claim 1, wherein in the film coating, a method for coating the TiN layer is that an alternating-current medium-frequency power supply is adopted by a magnetron sputtering coating process, argon is adopted as sputtering gas, nitrogen is adopted as reaction gas, a titanium target is sputtered, and the TiN layer is coated on the surface of the secondary treatment substrate, so that a glass substrate coated with the TiN layer is obtained;

the method for plating the first NiCr layer comprises the steps of sputtering a nickel-chromium alloy target material by using a direct current power supply and taking argon as sputtering gas through a magnetron sputtering coating process, and plating the first NiCr layer on the surface of the glass substrate plated with the TiN layer to obtain the glass substrate plated with the first NiCr layer;

The method for plating the first Ag layer comprises the steps of sputtering a silver target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and plating the first Ag layer on the surface of the glass substrate plated with the first NiCr layer to obtain the glass substrate plated with the first Ag layer;

the method for plating the second NiCr layer comprises the steps of sputtering a nickel-chromium alloy target material by using a direct current power supply and taking argon as sputtering gas through a magnetron sputtering coating process, and plating the second NiCr layer on the surface of the glass substrate plated with the first Ag layer to obtain the glass substrate plated with the second NiCr layer;

the method for plating the first ZnAlO layer comprises the steps of sputtering a zinc-aluminum alloy target material by adopting an alternating-current intermediate-frequency power supply through a magnetron sputtering coating process and taking argon as sputtering gas and oxygen as reaction gas, and plating the first ZnAlO layer on the surface of the glass substrate plated with the second NiCr layer to obtain the glass substrate plated with the first ZnAlO layer;

the method for plating the SiAl layer comprises the steps of sputtering an aluminum-silicon alloy target material by using an alternating-current medium-frequency power supply, taking argon as sputtering gas and taking nitrogen as reaction gas through a magnetron sputtering coating process, and plating the SiAl layer on the surface of the glass substrate plated with the first ZnAlO layer to obtain the glass substrate plated with the SiAl layer;

The method for plating the third NiCr layer comprises the steps of sputtering a nickel-chromium alloy target material by using a direct current power supply and taking argon as sputtering gas through a magnetron sputtering coating process, and plating the third NiCr layer on the surface of the glass substrate plated with the SiAl layer to obtain the glass substrate plated with the third NiCr layer;

the method for plating the second Ag layer comprises the steps of sputtering a silver target material by using a direct current power supply and argon as sputtering gas through a magnetron sputtering coating process, and plating the second Ag layer on the surface of the glass substrate plated with the third NiCr layer to obtain the glass substrate plated with the second Ag layer;

the method for plating the fourth NiCr layer comprises the steps of sputtering a nickel-chromium alloy target material by using a direct current power supply and taking argon as sputtering gas through a magnetron sputtering coating process, and plating the fourth NiCr layer on the surface of the glass substrate plated with the second Ag layer to obtain the glass substrate plated with the fourth NiCr layer;

the method for plating the second ZnAlO layer comprises the steps of sputtering a zinc-aluminum alloy target material by adopting an alternating-current intermediate-frequency power supply through a magnetron sputtering coating process and taking argon as sputtering gas and oxygen as reaction gas, and plating the second ZnAlO layer on the surface of the glass substrate plated with the fourth NiCr layer to obtain the glass substrate plated with the second ZnAlO layer;

The SiN layer plating method comprises the steps of sputtering a silicon target material by using an alternating-current medium-frequency power supply and argon as sputtering gas and nitrogen as reaction gas through a magnetron sputtering coating process, and plating the SiN layer on the surface of the glass substrate plated with the second ZnAlO layer to obtain a coated glass substrate.

5. The method for producing a low-emissivity coated glass according to claim 1, wherein in the coating, the TiN layer has a thickness of 50 to 60nm;

the thickness of the first NiCr layer is 2-3nm;

the thickness of the first Ag layer is 8-10nm;

the thickness of the second NiCr layer is 2-3nm;

the thickness of the first ZnAlO layer is 13-16nm;

the thickness of the SiAl layer is 55-65nm;

the thickness of the third NiCr layer is 2-3nm;

the thickness of the second Ag layer is 8-10nm;

the thickness of the fourth NiCr layer is 2-3nm;

the thickness of the second ZnAlO layer is 13-16nm;

the SiN layer thickness is 40-50nm.

6. The method for preparing low-emissivity coated glass according to claim 4, wherein in the coating of the film layer, the flow ratio of argon to nitrogen in the coating of the TiN layer is 500-550sccm:650-700SCCM;

plating a first NiCr layer, wherein the flow rate of argon is 500-600SCCM;

plating a first Ag layer, wherein the flow rate of argon is 500-600SCCM;

plating a second NiCr layer, wherein the flow rate of argon is 500-600SCCM;

In the first ZnAlO layer, the flow ratio of argon to oxygen is 700-750SCCM to 100-120SCCM;

in the SiAl layer plating, the flow ratio of argon to nitrogen is 500-550SCCM to 600-650SCCM;

plating a third NiCr layer, wherein the flow rate of argon is 500-600SCCM;

plating a second Ag layer, wherein the flow rate of argon is 500-600SCCM;

plating a fourth NiCr layer, wherein the flow rate of argon is 500-600SCCM;

in the second ZnAlO layer, the flow ratio of argon to oxygen is 700-750SCCM to 100-120SCCM; in the SiN coating, the flow ratio of argon to nitrogen is 500-550SCCM to 650-700SCCM.

7. The method for producing a low-emissivity coated glass according to claim 1, wherein in the post-treatment, a doctor-blading thickness of the coating agent on the surface of the coated glass substrate is controlled to be 300 to 350 μm;

after the doctor blade is finished, the standing time is 120-130h in the environment with the temperature of 20-25 ℃ and the relative humidity of 35-40%.

8. The method for preparing low-emissivity coated glass according to claim 1, wherein in the preparation of the coating agent, the weight ratio of the mixed solution to deionized water is 10-11:1;

the weight ratio of polymethyl methacrylate powder to titanate coupling agent 201 to 1, 2-diaminocyclohexane to modified polyether silicone oil to nano silicon dioxide to nano titanium dioxide to tetrahydrofuran is 30-32:0.9-1.1:6-7:5-6:3-3.2:1.5-2:250-270.

9. The method for preparing low-emissivity coated glass according to claim 1, wherein in the preparation of the coating agent, the modified polyether silicone oil is prepared by uniformly mixing polyether silicone oil and ethanol solution, heating to 45-55 ℃, and preserving heat; under the stirring condition, dripping a silane coupling agent KH-580 and a silane coupling agent KH-590 at the dripping rate of 0.1-0.15mL/min, continuously preserving heat and stirring after the dripping is completed, and evaporating ethanol in vacuum to obtain modified polyether silicone oil;

the volume ratio of the polyether silicone oil to the ethanol solution is 1:0.5-0.6;

10. A low emissivity coated glass produced by the method of any one of claims 1 to 9.