Glass green metal compound film preparation method and coated glass

Abstract

The invention discloses a glass green metal compound film layer preparation method and coated glass, the method comprises the following steps: S1, dissolving raw materials cobalt acetylacetonate, chromium acetylacetonate and titanyl acetylacetonate in an isopropanol or dichloromethane solvent according to a ratio to obtain a liquid-phase mixed coating solution; s2, spraying the liquid-phase coating solution on a high-temperature glass substrate through high-temperature spraying equipment; s3, the coating solution is subjected to high-temperature decomposition and deposition on the glass substrate, and a crystal film layer composed of cobalt, chromium and titanium oxides is formed; the coated glass comprises a glass substrate and a film layer, and has a sunlight control effect. The film layer provided by the invention is bright green, the problems that the traditional coated glass is single in color and not bright in color are solved, meanwhile, the problem that special glass such as borosilicate glass, microcrystalline glass and quartz glass is difficult to color is solved, the process is simple and easy to operate, the method is not only suitable for online implementation, but also suitable for offline assembly of a liquid phase spraying system for production, and the production cost is reduced. Application is flexible, and the application range is wide.

Description

Technical Field

[0001] The invention relates to the technical field of glass coating, and in particular to a method for preparing a glass green metal compound film layer and coated glass. Background Art

[0002] At present, the color film on glass is mostly coated by magnetron sputtering, online CVD coating of silicon film and other methods, the color is single and the color is not bright. However, the demand for glass decoration in modern buildings and home decoration is constantly increasing, and the existing coated glass can no longer fully meet the higher decorative requirements.

[0003] At the same time, existing special glasses, such as borosilicate glass, microcrystalline glass, and quartz glass, generally have the problem of difficulty in coloring. Because the melting temperature of special glasses is high, the heat permeability becomes poor after adding colorants, the melting rate decreases, and the glass quality decreases; while borosilicate glass, which can be produced by electric melting furnaces, is also difficult to color because the colorants easily react with electrodes. This makes it difficult to produce special color glasses at present.

[0004] Based on the above problems, it is urgent to develop a method for preparing a glass green metal compound film layer and coated glass to obtain coated glass with bright color and good visual effect and a method suitable for the production of special color glass. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing a green metal compound film layer on glass and coated glass in order to solve the problem that the existing coated glass has a single color and a dull color, and at the same time solve the problem that the current production of special color glass is difficult.

[0006] In order to solve the above technical problems, the technical solution adopted by the present invention is: a method for preparing a glass green metal compound film layer, comprising the following steps:

[0007] S1. The raw materials of cobalt acetylacetonate, chromium acetylacetonate, and titanium acetylacetonate are dissolved in isopropanol or dichloromethane solvent in proportion to obtain a liquid phase mixed coating solution;

[0008] S2. The liquid coating solution is sprayed on a high temperature glass substrate by a high temperature spraying device;

[0009] S3. The coating solution is decomposed and deposited on the glass substrate through high temperature, forming a crystalline film layer composed of cobalt, chromium and titanium oxides, which has a bright green appearance.

[0010] Preferably, in step S1, the molar ratio of the raw materials cobalt acetylacetonate, chromium acetylacetonate and titanium acetylacetonate is 1-2: 0.2-0.5: 1-2.

[0011] Preferably, in step S1, the concentration of the raw materials cobalt acetylacetonate, chromium acetylacetonate, titanium acetylacetonate and dichloromethane or isopropanol solution is 0.1-0.2 kg / L.

[0012] Preferably, the temperature of the high temperature glass substrate is 450-650°C.

[0013] Preferably, the preparation method is implemented in an off-line state, firstly heating the glass substrate to a desired temperature, and then performing a high-temperature spraying operation of the mixed coating solution.

[0014] Preferably, the preparation method is implemented online in the annealing A0 zone of the glass float line, and the high-temperature spraying operation of the mixed coating solution is performed by utilizing the residual temperature of the glass substrate produced online.

[0015] The present invention also provides a glass green metal compound film layer, which is composed of cobalt, chromium and titanium oxide, and has a main structure of a green crystalline film of Co-Ti-O.

[0016] Preferably, the thickness of the film layer is 30-80 nm, more preferably 40-60 nm.

[0017] The present invention also provides a coated glass, wherein the colored glass comprises a glass substrate and a film layer, and the glass substrate is selected from any one of ordinary float glass, borosilicate glass, microcrystalline glass, quartz glass and other special glasses.

[0018] Preferably, the glass substrate is made of colored glass of different colors, and is composited and stacked with the film layer to form a new colored glass.

[0019] The beneficial effects of the present invention are:

[0020] 1. Good film performance: The film provided by the present invention is green, has high brightness, and has good visual effects, which improves the problem of single color and dull color of traditional coated glass, and can fully meet the demand for glass decoration in modern buildings and home decoration. At the same time, the film provided by the present invention has good acid resistance, alkali resistance and wear resistance, and meets the national standard GB / T 18915.1-2013 testing standard; the film is formed at high temperature, has a stable crystal structure, and does not change color or be damaged after tempering; the coated glass using the film of the present invention has a stable green reflection color at any angle, and has a sunlight control effect.

[0021] 2. Good applicability: The present invention is not only applicable to ordinary float glass, but also can be applied to the production of special color glasses such as borosilicate glass, microcrystalline glass, quartz glass, etc., which solves the problem of difficulty in coloring special glass; at the same time, the preparation method provided by the present invention does not depend on the color of the substrate glass, and a new color film layer can be obtained by adjusting the raw material composition; and a new color glass can be obtained by adjusting the color of the glass substrate and superimposing it.

[0022] 3. The process is simple and easy to operate: the preparation method provided by the present invention is not only applicable to online implementation, using the annealing kiln area for production, but also can be produced by assembling a liquid phase spraying system offline, and is flexible in application. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.

[0024] Figure 1 This is a spectrum curve of the green film glass of the present invention.

[0025] Figure 2 It is a schematic diagram of the structure of the high temperature spraying equipment in the present invention.

[0026] Figure 3 It is a schematic structural diagram of the coated glass of the present invention.

[0027] In the figure: 10--spray gun; 20--material conduit; 30--high-pressure air pipe; 40--transmission chain; 50--conveying roller. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0029] The present invention provides a method for preparing a glass green metal compound film layer, comprising the following steps:

[0030] S1. The raw materials of cobalt acetylacetonate, chromium acetylacetonate, and titanium acetylacetonate are dissolved in isopropanol or dichloromethane solvent in proportion to obtain a liquid phase mixed coating solution;

[0031] S2. The liquid coating solution is sprayed on a high temperature glass substrate by a high temperature spraying device;

[0032] S3. The coating solution is decomposed and deposited on the glass substrate through high temperature, forming a crystalline film layer composed of cobalt, chromium and titanium oxides, which has a bright green appearance.

[0033] like Figure 2As shown, the high-temperature spraying equipment includes a spray gun 10 for spraying a mixed coating solution, the spray gun 10 is respectively connected to a material conduit 20 and a high-pressure air pipe 30, and the spray gun 10 is connected to a transmission chain 40, and the transmission chain 40 can drive the spray gun 10 to move laterally. During spraying, the mixed coating solution enters the spray gun 10 through the material conduit 20, and is sprayed on the high-temperature glass substrate through the spray gun 10. The glass substrate moves longitudinally under the drive of the conveying roller 50, and the spray gun 10 moves back and forth laterally under the drive of the transmission chain 40, thereby completing the uniform spraying operation of the entire glass substrate.

[0034] This embodiment adopts a thermal spraying method, using the heat of the high-temperature glass substrate and the surrounding environment to decompose the prepared mixed coating solution, forming cobalt, chromium, and titanium oxides on the surface of the glass substrate, forming a green crystal film layer with a main structure of Co-Ti-O. Compared with ordinary glass and traditional coated glass, the green glass produced by the present invention has significant brightness and color advantages.

[0035] In the present invention, the metal compound is pyrolyzed on the glass substrate to form a green metal compound film layer. After high-temperature film formation, the film layer structure is more stable, and has a stable green reflection color at any angle, and has a sunlight control effect; it also has stable weather resistance and wear resistance; after tempering, the film layer does not change color and is not damaged; and the present invention has a simple structure, low production cost, easy operation, and is suitable for mass production.

[0036] As a preferred embodiment, in step S1, the molar ratio of the raw materials cobalt acetylacetonate, chromium acetylacetonate, and titanium acetylacetonate is 1-2: 0.2-0.5: 1-2.

[0037] As a preferred embodiment, in step S1, the mixing concentration of the raw materials cobalt acetylacetonate, chromium acetylacetonate, titanium acetylacetonate and dichloromethane or isopropanol solution is 0.1-0.2 Kg / L.

[0038] As a preferred embodiment, in step S2, the temperature of the high temperature glass substrate is controlled at 450-650° C. At this temperature, the mixed coating solution can be fully decomposed and vaporized to ensure complete reaction and decomposition of the raw materials, while also avoiding deformation of the glass caused by excessive temperature.

[0039] As a preferred embodiment, in step S3, the thickness of the crystal film layer is 30-80nm, more preferably, the thickness of the film layer is 40-60nm, which is at 1 / 4 wavelength of the reflective film, has good optical properties, and avoids the occurrence of reflective interference colors.

[0040] Embodiment 1:

[0041] The raw materials of cobalt acetylacetonate, chromium acetylacetonate, and titanium acetylacetonate were mixed in a molar ratio of 1:0.2:1 and dissolved in dichloromethane to form a mixed coating solution with a mixed concentration of 0.15 Kg / L. The borosilicate glass substrate was heated to 630°C, and the raw materials were sprayed on the surface of the high-temperature glass substrate through a high-temperature spraying device to obtain an emerald green film glass. Its spectral curve is as follows Figure 1 As shown, the visible light transmittance is 69.22% and the visible light reflectivity of the film is 27.74%.

[0042] Comparative Example 1-1:

[0043] The raw materials of cobalt acetylacetonate, chromium acetylacetonate, and titanium acetylacetonate were mixed in a molar ratio of 1:0.2:1 and dissolved in dichloromethane to form a mixed coating solution with a mixed concentration of 0.15 Kg / L. The borosilicate glass substrate was heated to 500°C, and the raw materials were sprayed on the surface of the high-temperature glass substrate through a high-temperature spraying device to obtain emerald green film glass.

[0044] Comparative Example 1-2:

[0045] The raw materials of cobalt acetylacetonate, chromium acetylacetonate, and titanium acetylacetonate were mixed in a molar ratio of 5:0.2:1 and dissolved in dichloromethane to form a mixed coating solution with a mixed concentration of 0.15 Kg / L. The borosilicate glass substrate was heated to 630°C, and the coating solution was sprayed on the surface of the high-temperature glass substrate through a high-temperature spraying device. The film layer did not show green, but was brown-green.

[0046] Embodiment 2:

[0047] The raw materials of cobalt acetylacetonate, chromium acetylacetonate, and titanium acetylacetonate were mixed in a molar ratio of 2:0.5:2 and dissolved in isopropanol to form a mixed coating solution with a mixing concentration of 0.2 Kg / L. The borosilicate glass substrate was heated to 480°C, and the high-temperature spraying equipment sprayed the coating solution on the surface of the high-temperature glass substrate to obtain emerald green film glass.

[0048] Embodiment 3:

[0049] The raw materials of cobalt acetylacetonate, chromium acetylacetonate, and titanium acetylacetonate are mixed in a molar ratio of 1:0.2:1, and dissolved in dichloromethane to form a mixed coating solution, and the mixed concentration is 0.15 Kg / L. The coating solution preparation method of this embodiment is consistent with that of embodiment 1, except that the coating process of this embodiment is carried out in the annealing A0 zone of the float glass production line, the glass substrate is white glass, the temperature is 600°C, and the high-temperature spraying equipment sprays the coating solution on the surface of the high-temperature glass substrate to obtain green coated glass.

[0050] Embodiment 4:

[0051] The raw materials of cobalt acetylacetonate, chromium acetylacetonate, and titanium acetylacetonate are mixed in a molar ratio of 1: 0.2: 1, dissolved in dichloromethane to form a mixed coating solution, the mixed concentration is 0.15 Kg / L, and the coating process is carried out in the annealing A0 zone of the float glass production line. This embodiment is consistent with the coating solution preparation method and coating area in Example 3, the difference is that the glass substrate in this embodiment is lake blue glass, the temperature is 580°C, and the high-temperature spraying equipment sprays the coating solution on the surface of the high-temperature glass substrate to obtain cyan coated glass.

[0052] The performance data of the coated glass in the embodiments and comparative examples are shown in Table 1:

[0053] Table 1

[0054] performance Visible light transmittance Wear resistance Acid resistance Alkali resistance L* a* b* Example 1 69.22% 0.5% 1.8% 0.6% 86.63 -1.47 0.17 Example 2 67.90% 0.7% 2.3% 1.1% 82.85 -2.77 1.9 Example 3 67.50% 0.1% 0.5% 0% 80.20 -9.5 1.23 Example 4 50.08% 0.3% 0.8% 0.1% 72.70 -2.23 2.30 Comparative Example 1-1 64.60% 2.3% 3.6% 0.6% 84.70 -1.10 1.24 Comparative Example 1-2 66.15% 1.1% 1.4% 0.2% 77.54 -0.67 -1.46

[0055] In the above determination method, acid resistance, alkali resistance and abrasion resistance are determined according to the GB / T 18915.1-2013 test standard. In the table, L*, a*, and b* represent the three coordinate axes of the three-dimensional color model. Among them, L* is the lightness coordinate axis of the color; a* is the red-green coordinate axis, a* is "+" for red, and a* is "-" for green; b* is the yellow-blue coordinate axis, b* is "+" for yellow, and b* is "-" for blue.

[0056] It can be seen from Table 1 that the glass green metal oxide film layer prepared by the preparation method provided by the present invention is green and has high brightness. In Examples 1, 2, and 3, the film layers all present a green color with high brightness. In Example 3, the online spraying temperature is stable, the crystallization is complete, and the corrosion resistance is better than that of offline spraying. In Example 4, a green film is sprayed on lake blue glass, and a cyan coated glass is formed by composite superposition. It can be seen that the green film can be composited with colored glass to superimpose a new color system glass. In Comparative Examples 1-2, the cobalt content is increased, exceeding the proportional range. As the cobalt content increases, the yellow-brown tone of the film layer increases, and as a result, the film layer presents a brown-green color.

[0057] It should be noted that the method for preparing the green metal oxide film layer on glass provided by the present invention can be implemented in an offline state. After the glass substrate is heated to the required temperature, the high-temperature spraying operation of the mixed coating solution can be performed. Therefore, the preparation method can re-coat the offline glass, and the operation is more flexible. In addition, the preparation method can also be implemented online in the annealing A0 zone of the glass float line. The high-temperature spraying operation of the mixed coating solution can be performed by using the residual temperature of the glass substrate produced online, thereby eliminating the step of reheating the glass substrate, saving energy consumption, realizing continuous batch production, and ensuring production efficiency.

[0058] At the same time, the present invention also provides a glass green metal oxide film layer prepared by the above preparation method, wherein the film layer is composed of cobalt, chromium, and titanium oxides, and its main structure is a green crystalline film of Co-Ti-O. Preferably, the thickness of the film layer is 30-80nm. More preferably, the thickness of the film layer is 40-60nm.

[0059] The present invention also provides a coated glass, such as Figure 3 As shown, the coated glass comprises a glass substrate and a film layer, and the film layer is prepared by the above-mentioned preparation method. The coated glass of the present invention has a sunlight control effect, and has chemical stability, weather resistance, and wear resistance; the film layer does not change color or be damaged after being tempered; and the present invention has a simple structure, low production cost, easy operation, and is suitable for mass production.

[0060] Preferably, the glass substrate can be ordinary float glass, or special glass such as borosilicate glass, microcrystalline glass, quartz glass, etc., which has a wide range of applications and solves the problem of difficulty in coloring traditional special glass. At the same time, the glass substrate can be made of white glass to produce green coated glass; the glass substrate can also be made of different color glasses, which are compounded and superimposed with the film layer of the present invention to form new color glass. For example, the glass substrate is made of lake blue glass, which is compounded with the green metal oxide film layer of the present invention to produce cyan coated glass.

[0061] The above disclosure is only a specific embodiment of the present invention, but the present invention is not limited thereto. For ordinary technicians in this field, without departing from the principle of the present invention, any modifications made should be deemed to belong to the protection of the present invention.

Claims

1. A method for preparing a glass green metal compound film layer, characterized in that: The process includes the following steps: S1. The raw materials of cobalt acetylacetonate, chromium acetylacetonate, and titanium acetylacetonate are dissolved in isopropanol or dichloromethane solvent in proportion to obtain a liquid phase mixed coating solution; S2. The liquid coating solution is sprayed on a high temperature glass substrate by a high temperature spraying device; S3. The coating solution is decomposed and deposited on the glass substrate through high temperature, forming a crystalline film layer composed of cobalt, chromium and titanium oxides, which has a bright green appearance.

2. The method for preparing a glass green metal compound film layer according to claim 1, characterized in that: In the step S1, the molar ratio of the raw materials cobalt acetylacetonate, chromium acetylacetonate and titanium acetylacetonate is 1-2: 0.2-0.5: 1-2.

3. The method for preparing a glass green metal compound film layer according to claim 1, characterized in that: In the step S1, the mixing concentration of the raw materials cobalt acetylacetonate, chromium acetylacetonate, titanium acetylacetonate and dichloromethane or isopropanol solution is 0.1-0.2 kg / L.

4. The method for preparing a glass green metal compound film layer according to claim 1, characterized in that: The temperature of the high temperature glass substrate is 450-650°C.

5. The method for preparing a glass green metal compound film layer according to claim 1, characterized in that: The preparation method is implemented in an off-line state, firstly heating the glass substrate to a required temperature, and then performing a high-temperature spraying operation of the mixed coating solution.

6. The method for preparing a glass green metal compound film layer according to claim 1, characterized in that: The preparation method is implemented online in the annealing A0 zone of a glass float line, and the high-temperature spraying operation of the mixed coating solution is performed by utilizing the residual temperature of the glass substrate produced online.

7. A glass green metal compound film layer, characterized in that: The film layer is prepared by the preparation method described in any one of claims 1 to 6, and is composed of cobalt, chromium, and titanium oxides, and its main structure is a green crystalline film of Co-Ti-O.

8. The glass green metal compound film layer according to claim 7, characterized in that: The thickness of the film layer is 30-80 nm.

9. A coated glass, comprising a glass substrate and a film layer, characterized in that: The film layer is prepared by the preparation method described in any one of claims 1 to 6, and the glass substrate can be selected from common float glass, borosilicate glass, microcrystalline glass, and quartz glass.

10. The coated glass according to claim 9, characterized in that: The glass substrate is made of colored glass of different colors and is compounded and stacked with the film layer to form a new colored glass.

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