CN115368025A - Anti-pollution self-cleaning glass substrate and preparation method thereof - Google Patents
Anti-pollution self-cleaning glass substrate and preparation method thereof Download PDFInfo
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- CN115368025A CN115368025A CN202210693223.5A CN202210693223A CN115368025A CN 115368025 A CN115368025 A CN 115368025A CN 202210693223 A CN202210693223 A CN 202210693223A CN 115368025 A CN115368025 A CN 115368025A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/112—Deposition methods from solutions or suspensions by spraying
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention relates to G02B1, in particular to a stain-resistant self-cleaning glass substrate and a preparation method thereof. The anti-pollution self-cleaning glass substrate comprises a composite coating and a glass substrate. The anti-fouling self-cleaning glass substrate provided by the invention can decompose organic pollutants such as oil stains and the like attached to the surface, so that the adhesive force between the pollutants and the substrate is weakened, the pollutants are easy to blow away by wind or rain, water easily enters the gap between the pollutants and the substrate, the pollutants are easy to be washed away by water, a cleaning agent is not needed, the glass substrate can be effectively cleaned, the impact on the environment is reduced, in addition, the composite coating enables the glass substrate to have lower surface resistance, and the electrostatic adsorption quantity of dust generated by the environment can be obviously reduced.
Description
Technical Field
The invention relates to G02B1, in particular to a stain-resistant self-cleaning glass substrate and a preparation method thereof.
Background
The glass is cleaned regularly, so that the maintenance cost of the glass is increased, and the time and the labor are consumed. With the progress of social science and technology, people gradually start to use a self-cleaning technology to replace the traditional cleaning method.
Patent No. CN110240816B provides a transparent self-cleaning anti-dust deposition coating material and a preparation method thereof, titanium oxide sol and zinc oxide sol are compounded, the obtained mixed sol is sprayed on the surface of a glass sheet, and high-temperature calcination is carried out, so that the glass has the anti-dust deposition performance. Patent No. CN110250169B provides a silver-loaded nano titanium dioxide sol, a preparation method and a preparation method thereof, which control the irradiation intensity during photocatalysis, so that the silver is dispersed more uniformly in the sol and has smaller particle size.
Therefore, in order to obtain self-cleaning glass, most of people need to spray the spray paint on the glass and then carry out high-temperature treatment on the glass, the process is complex, the spray paint cannot be directly used in daily life, most of researches are based on common glass substrates, and few reports are provided for toughened glass with higher internal stress.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides an anti-fouling self-cleaning glass substrate comprising a composite coating and a glass substrate.
As a preferable technical scheme of the invention, the raw materials of the composite coating comprise a solution A and a solution B.
As a preferable technical scheme of the invention, the raw materials of the solution A comprise organic titanium salt and absolute ethyl alcohol, and the weight ratio of the organic titanium salt to the absolute ethyl alcohol in the solution A is (5.3-7.2): (14.6-15.9).
Preferably, the organic titanium salt is n-butyl titanate.
Preferably, the preparation method of the solution A comprises the following steps: adding absolute ethyl alcohol into a beaker, starting magnetic stirring, adding organic titanium salt into the beaker, and keeping the magnetic stirring for 20min.
As a preferred technical scheme of the invention, the raw materials of the solution B comprise organic acid, absolute ethyl alcohol and deionized water, wherein the weight ratio of the organic acid to the absolute ethyl alcohol to the deionized water in the solution B is (3.8-4.4): (14.6-15.9): (1.3-2.7).
Preferably, the organic acid is glacial acetic acid.
Preferably, the preparation method of the solution B comprises the following steps: mixing absolute ethyl alcohol and deionized water, adding acetic acid into the mixed solution, and magnetically stirring for 15-25min.
As a preferable technical scheme of the invention, the weight ratio of the solution A to the solution B is (0.8-1.2): 1.
as a preferable technical scheme, the raw material of the composite coating also comprises silica sol.
As a preferable technical scheme of the invention, the silica sol is prepared by silane modification.
As a preferred technical scheme of the invention, the silane is selected from one or more of methyl triethoxysilane, propyl triethoxysilane, tetraethoxysilane, N-octyl triethoxysilane and dodecyl triethoxysilane.
Preferably, the silanes are methyltriethoxysilane and dodecyltriethoxysilane.
Further preferably, the weight ratio of the methyl triethoxysilane to the dodecyl triethoxysilane in the silane is 1: (2-4).
In order to improve the stability of the silica sol when the silica sol is used in a product and simultaneously enable the obtained composite coating to have a quick-drying function, the applicant modifies the silica sol by using a silane coupling agent and then mixes the modified silica sol with titanium sol, and surprisingly discovers that when methyl triethoxysilane and dodecyl triethoxysilane are added, the coating can not only improve the problems, but also directly use the coating in daily life while maintaining the cleaning performance, and the coating is used on a glass substrate, especially a toughened glass substrate, so that the later-stage manual cleaning frequency of glass is greatly reduced, the later-stage maintenance and cleaning are not needed 7-10 years after the coating is sprayed on the toughened glass, and the adhesive force of the coating is also improved. The reason for this is probably that the addition of methyl triethoxysilane and dodecyl triethoxysilane with specific chain lengths affects the molecular structure of the formed sol, and the hydroxyl groups in the original silica sol and the hydroxyl groups hydrolyzed after modification act synergistically to change steric hindrance, so that the film-forming property is improved when the obtained coating is sprayed on the surface of a glass substrate. The above-mentioned effects are achieved in particular when the weight ratio of methyltriethoxysilane to dodecyltriethoxysilane is 1: the case (2-4) is more excellent.
Preferably, the preparation method of the silica sol is to take acid silica and drop silane, wherein the weight ratio of the acid silica to the silane is 50: (0.03-0.06), controlling the silane to completely drip in 7-9min, reacting at 80 ℃ for 4-5h, cooling to 25 ℃ to obtain mixed sol, adding toluene for extraction to remove water to obtain silica sol, wherein the volume ratio of the mixed sol to the toluene is 1:2.
it is further preferred that the particle size of the acidic silica is less than 30nm.
Preferably, the preparation method of the composite coating comprises the following steps: (1) Under magnetic stirring, dropwise adding the B liquid into the A liquid, after dropwise adding, continuing stirring for 25min, and sealing and aging for 10h to obtain a first mixed liquid; (2) mixing the first mixed solution and the silica sol according to the following ratio (1-1.2): (4.7-5.4), stirring, standing and aging for 12h.
As a preferable technical scheme of the invention, the glass substrate is toughened glass.
The invention provides a preparation method of an anti-pollution self-cleaning glass substrate, which comprises the following steps: and spraying the composite coating on the surface of the glass substrate by using a spray gun, wherein the diameter of the spray gun is 0.3-0.5mm, and the spraying distance is 15-20cm, so as to obtain the glass substrate.
Preferably, the spray gun is connected with an air compressor, and the power of the air compressor is 2.4-2.6hp.
Further preferably, the power of the air compressor is 2.5hp.
Compared with the prior art, the invention has the following beneficial effects:
when the methyl triethoxysilane and the dodecyl triethoxysilane are added, the spray coating can be directly used in daily life while maintaining the cleaning performance, and is used on a glass substrate, especially a toughened glass substrate, so that the later-stage manual cleaning frequency of the glass is greatly reduced, the later-stage maintenance and cleaning are not required 7-10 years after the spray coating is carried out on the toughened glass, and the adhesive force of the coating is also improved. The particle size of the acidic silicon dioxide is less than 30nm, and the acidic silicon dioxide can be well acted with titanium dioxide sol after being modified by silane, so that the film forming effect of the coating after spraying is improved, and the coating is not easy to crack. The anti-fouling self-cleaning glass substrate provided by the invention can decompose organic pollutants such as oil stains and the like attached to the surface, so that the adhesive force between the pollutants and the substrate is weakened, the pollutants are easy to blow away by wind or rain, water easily enters the gap between the pollutants and the substrate, the pollutants are easy to be washed away by water, a cleaning agent is not needed, the glass substrate can be effectively cleaned, the impact on the environment is reduced, in addition, the composite coating enables the glass substrate to have lower surface resistance, and the electrostatic adsorption quantity of dust generated by the environment can be obviously reduced.
Drawings
FIG. 1 is an electron micrograph of a composite coating obtained in example 1;
FIG. 2 is the appearance of example 1 in performance test 4;
FIG. 3 is the appearance of example 5 in performance test 4;
FIG. 4 is the appearance of example 1 in performance test 5;
fig. 5 is the appearance of example 5 in performance test 5.
Detailed Description
Examples
The compositions of the examples were prepared from commercially available raw materials, wherein the acidic silica sols of examples 1 and 4 were obtained from different sources, example 1 was obtained from CRYSTAL, VK-S01A, and had particle sizes of 15. + -.5 nm, example 4 was obtained from HUIKI and Yongcheng, and was obtained from SDW-3030, and had particle sizes of 60 to 90nm, methyltriethoxysilane was obtained from Kyozhou Jeccard chemical Co., ltd., dodecyltriethoxysilane was obtained from Youpu chemical, N-octyltriethoxysilane was obtained from Heng chemical, and toughened glass was obtained from Brilliant glass.
Example 1
The present example provides an anti-fouling, self-cleaning glass substrate comprising a composite coating and a glass substrate.
The raw materials of the composite coating comprise a liquid A and a liquid B.
The raw materials of the solution A comprise organic titanium salt and absolute ethyl alcohol, wherein the weight ratio of the organic titanium salt to the absolute ethyl alcohol in the solution A is 5.8:15.2. the organic titanium salt is n-butyl titanate.
The preparation method of the solution A comprises the following steps: adding absolute ethyl alcohol into a beaker, starting magnetic stirring, adding organic titanium salt into the beaker, and keeping the magnetic stirring for 20min.
The raw materials of the solution B comprise organic acid, absolute ethyl alcohol and deionized water, wherein in the solution B, the weight ratio of the organic acid to the absolute ethyl alcohol to the deionized water is 4:15.2:2.2.
the organic acid is glacial acetic acid.
The preparation method of the solution B comprises the following steps: after mixing absolute ethyl alcohol and deionized water, adding acetic acid into the mixed solution, and magnetically stirring for 20min.
The weight ratio of the solution A to the solution B is 0.9:1.
the raw materials of the composite coating also comprise silica sol. The silica sol is prepared by silane modification.
The silane is methyl triethoxysilane and dodecyl triethoxysilane.
In the silane, the weight ratio of the methyl triethoxysilane to the dodecyl triethoxysilane is 1:3.
the preparation method of the silica sol comprises the steps of dropwise adding silane into acidic silica, wherein the weight ratio of the acidic silica to the silane is 50:0.04, controlling the silane to be dripped in 8min, reacting at 80 ℃ for 4-5h, cooling to 25 ℃ to obtain mixed sol, adding toluene for extraction to remove water to obtain silica sol, wherein the volume ratio of the mixed sol to the toluene is 1:2.
the preparation method of the composite coating comprises the following steps: (1) Under magnetic stirring, dropwise adding the solution B into the solution A, after dropwise adding, continuing stirring for 25min, and sealing and aging for 10h to obtain a first mixed solution; (2) mixing the first mixed solution with silica sol according to a ratio of 1.1:5, stirring, standing and aging for 12 hours.
The glass substrate is toughened glass.
The embodiment also provides a preparation method of the anti-pollution self-cleaning glass substrate, which comprises the following steps: and (3) spraying the composite coating on the surface of the glass substrate by using a spray gun, wherein the diameter of the spray gun is 0.4mm, and the spraying distance is 15cm, so as to obtain the coating.
The spray gun is connected with an air compressor, and the power of the air compressor is 2.5hp.
Example 2
The present example provides an anti-fouling self-cleaning glass substrate, differing from example 1 in that the weight ratio of methyltriethoxysilane to dodecyltriethoxysilane in the silane is 1:3.5.
example 3
The embodiment provides a stain-resistant self-cleaning glass substrate, and is different from the embodiment 1 in that the weight ratio of organic titanium salt to absolute ethyl alcohol in the solution A is 6:15.8.
example 4
The embodiment provides a stain-resistant self-cleaning glass substrate, which is different from the embodiment 1 in that the source of the acid silicon dioxide is different, and the preparation method of the composite coating comprises the following steps: (1) Under magnetic stirring, dropwise adding the B liquid into the A liquid, after dropwise adding, continuing stirring for 25min, and sealing and aging for 10h to obtain a first mixed liquid; (2) mixing the first mixed solution with silica sol according to the ratio of 1:4.9, stirring, standing and aging for 12 hours.
Example 5
This example provides an anti-fouling self-cleaning glass substrate, differing from example 1 in that the silanes added are methyl triethoxysilane and N-octyl triethoxysilane. In the silane, the weight ratio of the methyl triethoxysilane to the N-octyl triethoxysilane is 1:4.1.
and (3) performance testing:
1. and (3) morphology testing: the composite coating obtained in example 1 was subjected to Transmission Electron Microscopy (TEM), and as can be seen from fig. 1, the structure was columnar-like.
2. And (3) antistatic test: the antistatic performance (obtained from sample ESD 20K) of the glass substrate and the toughened glass obtained in example 1 was tested by an antistatic tester, and the result shows that the glass substrate obtained in example 1 has better antistatic effect than the toughened glass.
3. And (3) testing the adhesive force: the adhesion of the composite coating on the glass substrate obtained in examples 1 to 5 was tested in accordance with GB/T9286-1998, and after the test, it was observed whether the surface of the glass substrate was flat and cracked, and the results are shown in Table 1:
TABLE 1
4. And (3) testing the stability of the appearance effect of the glass substrate: after the glass substrates obtained in examples 1 and 5 were left to stand for 12 months and washed with water, the appearance of example 1, as shown in fig. 2, and the appearance of the glass substrate of example 5, as shown in fig. 3, revealed that the glass substrate obtained in example 1 had remarkable self-cleaning properties.
5. Testing the self-cleaning performance of the glass substrate: when 0.005g of graphite powder was applied to the surfaces of the glass substrates of examples 1 and 4 and 2mL of water was added, the appearance of example 1 is shown in fig. 4, and the appearance of the glass substrate of example 5 is shown in fig. 5, and it can be seen that the glass substrate obtained in example 1 has a remarkable self-cleaning property.
Claims (10)
1. The anti-pollution self-cleaning glass substrate is characterized by comprising a composite coating and a glass substrate.
2. The anti-fouling self-cleaning glass substrate according to claim 1, wherein the raw materials of the composite coating comprise a solution A and a solution B.
3. The anti-fouling self-cleaning glass substrate according to claim 2, wherein the raw materials of the solution A comprise organic titanium salt and absolute ethyl alcohol, and the weight ratio of the organic titanium salt to the absolute ethyl alcohol in the solution A is (5.3-7.2): (14.6-15.9).
4. The anti-fouling self-cleaning glass substrate according to claim 2, wherein the raw materials of the solution B comprise organic acid, anhydrous ethanol and deionized water, and the weight ratio of the organic acid to the anhydrous ethanol to the deionized water in the solution B is (3.8-4.4): (14.6-15.9): (1.3-2.7).
5. An anti-fouling self-cleaning glass substrate according to any one of claims 2 to 4, wherein the weight ratio of the solution A to the solution B is (0.8-1.2): 1.
6. the stain resistant self-cleaning glass substrate of claim 5 wherein the composite coating materials further comprise silica sol.
7. The anti-fouling self-cleaning glass substrate according to claim 6, wherein the silica sol is prepared by silane modification.
8. An anti-fouling self-cleaning glass substrate according to claim 7, wherein the silane is selected from one or more of methyltriethoxysilane, propyltriethoxysilane, tetraethoxysilane, N-octyltriethoxysilane, dodecyltriethoxysilane.
9. An anti-fouling self-cleaning glass substrate as claimed in any one of claims 1 to 8, wherein the glass substrate is toughened glass.
10. A method of preparing an anti-fouling self-cleaning glass substrate according to any one of claims 1 to 9, characterised in that the method comprises: and spraying the composite coating on the surface of the glass substrate by using a spray gun, wherein the diameter of the spray gun is 0.3-0.5mm, and the spraying distance is 15-20cm, so as to obtain the glass substrate.
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2022
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Address after: Room 106, 1st Floor, Building C1, No. 88, Dongchang Road, Suzhou Industrial Park, Suzhou Area, China (Jiangsu) Pilot Free Trade Zone, 215000 Jiangsu Province Applicant after: Suzhou Jingcheng Materials Co.,Ltd. Address before: 200120 Room 106, 1st Floor, Building C1, No. 88, Dongchang Road, Suzhou Industrial Park, Suzhou Area, China (Jiangsu) Pilot Free Trade Zone, Pudong New Area, Shanghai Applicant before: Suzhou Jingcheng Materials Co.,Ltd. |