Glass surface functional film and preparation and application thereof

Abstract

The invention discloses a glass surface functional film as well as preparation and application thereof, and belongs to the technical field of film materials. A preparation method of a glass surface functional film comprises the following steps: S1, uniformly mixing ammonium persulfate, lauryl sodium sulfate and deionized water, heating and stirring to obtain a dispersion liquid; mixing the modified silicon dioxide nanoparticles, aluminum oxide nanoparticles and a solvent, performing ultrasonic treatment, adding chitosan, and stirring to obtain a mixed solution; mixing the dispersion liquid and the mixed liquid, and continuously heating and stirring to obtain a prepolymer; adding an initiator into the prepolymer, and uniformly stirring to obtain a modified silicon dioxide nanoparticle / aluminum oxide polymer; and S2, in an inert gas atmosphere, forming a functional film on the surface of the pretreated base material by using the modified silicon dioxide nanoparticle / aluminum oxide polymer through a magnetic control coating method.

Description

Technical Field

[0001] The invention belongs to the technical field of membrane materials, and in particular relates to a glass surface functional film and a preparation and application thereof. Background Art

[0002] Glass surface functional film refers to a layer of thin film material with special functions deposited or coated on the glass surface by physical or chemical methods, thus giving the glass new properties, such as optical, electronic, protective, self-cleaning, antibacterial and other functions. These films can change the optical properties of glass (such as transmittance, reflectivity), improve wear resistance and hardness, enhance antistatic properties, or achieve special functions such as antibacterial and self-cleaning.

[0003] The patent application with publication number CN106746736A discloses a super-hydrophobic glass coating and a preparation method thereof, wherein the coating includes a nanoporous glass film and a low surface energy hydrophobic film attached to the glass surface from the inside to the outside, but the hydrophobic coating material mainly adopts fluorine-containing resin, and the preparation process is cumbersome, and the process conditions are relatively harsh, and the curing temperature exceeds 300 ° C, and there is a risk of harm and pollution to the human body and the environment, and the fluorine compound is expensive and the preparation cost is high. In addition, adding particles such as silicon dioxide to the glass surface to increase the microscopic roughness of the glass substrate surface can also achieve the purpose of hydrophobicity, such as the patent application with publication number CN105670393A discloses a method for preparing a super-hydrophobic coating by a cellulose nanocrystal / silicon dioxide composite template method, and the application belongs to a heterogeneous addition method, because the surface energy of particles such as silicon dioxide themselves is high and the brittleness is large, the mechanical properties of the coating are reduced.

[0004] Therefore, it is very necessary to prepare a functional glass film that has good wear resistance and hydrophobicity as well as excellent mechanical properties. Summary of the invention

[0005] The purpose of the present invention is to provide a glass surface functional film and its preparation and application, so as to improve the wear resistance of the film.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A method for preparing a glass surface functional film comprises the following steps:

[0008] S1, mixing silica nanoparticles, a silane coupling agent and deionized water, adjusting the pH, heating and stirring, washing and dialyzing to obtain modified silica nanoparticles;

[0009] S2, ammonium persulfate, sodium dodecyl sulfate and deionized water are mixed uniformly, heated and stirred to obtain a dispersion; modified silica nanoparticles, alumina nanoparticles and a solvent are mixed, ultrasonicated, chitosan is added and stirred to obtain a mixed solution; the dispersion and the mixed solution are mixed, and the heating and stirring are continued to obtain a prepolymer; an initiator is added to the prepolymer and stirred uniformly, centrifuged, washed, and dried to obtain a modified silica nanoparticle / alumina polymer;

[0010] S3. In an inert gas atmosphere, the modified silica nanoparticles / alumina polymer is formed into a functional film on the surface of the pretreated substrate by a magnetron coating method.

[0011] Furthermore, the usage ratio of the silicon dioxide nanoparticles, the silane coupling agent and the deionized water is (6-10) g: (1-1.5) g: (35-40) mL.

[0012] Furthermore, the silane coupling agent is one or a combination of 3-(methacryloyloxy)propyltrimethoxysilane, monoethoxysilane-PEG-carboxylic acid and 2-(carboxymethylthio)ethyltrimethylsilane.

[0013] Furthermore, the pH is adjusted to 3-4.

[0014] Furthermore, the usage ratio of ammonium persulfate, sodium dodecyl sulfate and deionized water in the dispersion is (0.2-0.4) g: (15-25) g: (80-120) g.

[0015] Furthermore, the ratio of the modified silica nanoparticles, the alumina nanoparticles, the solvent and the chitosan in the mixed solution is (8-10) g: (12-15) g: (80-100) g: (1-2) g.

[0016] Furthermore, the solvent is a mixture of acetic acid and ethanol in a volume ratio of 1:1.

[0017] Furthermore, the heating and stirring is stirring at 60-80° C. for 2-4 hours.

[0018] Furthermore, the initiator is ammonium persulfate, and the amount of the initiator added is 1% to 2% of the weight of the prepolymer.

[0019] Furthermore, the surface of the substrate after the pretreatment is clean and free of pollution.

[0020] Furthermore, the thickness of the film is 50-70 μm.

[0021] A glass surface functional film is prepared by the above preparation method.

[0022] Furthermore, the glass surface functional film is used in LOW-E glass.

[0023] Beneficial effects of the present invention:

[0024] (1) The present invention provides a glass surface functional film, which improves the modified silica nanoparticle / alumina polymer formula; modifies the silica nanoparticles, optimizes the compatibility of the silica nanoparticles and the alumina nanoparticles; improves the dispersibility of the silica nanoparticles in the film, and enhances the wear resistance of the functional film.

[0025] (2) The modified nano-silica used in the present invention can give the film the characteristics of reducing ultraviolet light transmittance and higher transparency due to its own characteristics; and the aluminum oxide used has higher hardness and wear resistance, which not only further improves the wear resistance of the film, but also improves the dispersibility of the nano-silica through electrostatic adsorption with the modified silica nanoparticles and reduces the migration of silica. DETAILED DESCRIPTION

[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] Example 1

[0028] This embodiment provides a glass surface functional film, which is prepared by the following steps:

[0029] S1. 8 g of silica nanoparticles, 1.5 g of 3-(methacryloyloxy)propyltrimethoxysilane and 40 mL of deionized water were mixed, the pH was adjusted to 4, stirred in a 60° C. water bath for 4 h, washed three times with a 1:1 ether-acetone mixture, centrifuged at a speed of 10,000 r / min, dialyzed with a dialysis bag with a molecular weight cutoff of 10,000 for 5 days, and the deionized water was replaced every day to obtain modified silica nanoparticles;

[0030] S2, 0.3g ammonium persulfate, 20g sodium dodecyl sulfate and 100g deionized water were mixed evenly, and stirred at 80°C for 2h to obtain a dispersion; 9g modified silica nanoparticles, 15g alumina nanoparticles and 100g acetic acid and ethanol in a volume ratio of 1:1 were mixed, ultrasonicated, and 1.5g chitosan was added and stirred to obtain a mixed solution; the dispersion and the mixed solution were mixed, and heating and stirring were continued to obtain a prepolymer; ammonium persulfate was added to the prepolymer and stirred evenly, and the amount of initiator added was 1.5% of the weight of the prepolymer, centrifuged, washed, and dried to obtain a modified silica nanoparticle / alumina polymer;

[0031] S3. In an inert gas atmosphere, a functional film is formed on the surface of a pretreated substrate by a magnetron coating method using modified silicon dioxide nanoparticles / aluminum oxide polymers. The thickness of the functional film is 60 μm.

[0032] The functional film prepared as above is applied to LOW-E glass.

[0033] Example 2

[0034] Compared with Example 1, this embodiment differs in that the ratio of raw materials in the S2 dispersion is changed, and the specific implementation steps are as follows:

[0035] S2, 0.2g ammonium persulfate, 21g sodium dodecyl sulfate and 100g deionized water were mixed evenly, and stirred at 80°C for 2h to obtain a dispersion; 9g modified silica nanoparticles, 15g alumina nanoparticles and 100g acetic acid and ethanol in a volume ratio of 1:1 were mixed, ultrasonicated, and 1.5g chitosan was added and stirred to obtain a mixed solution; the dispersion and the mixed solution were mixed, and heating and stirring were continued to obtain a prepolymer; ammonium persulfate was added to the prepolymer and stirred evenly, and the amount of initiator added was 1.5% of the weight of the prepolymer, centrifuged, washed, and dried to obtain a modified silica nanoparticle / alumina polymer;

[0036] The remaining raw materials and preparation process remain the same as in Example 1.

[0037] Example 3

[0038] Compared with Example 1, this embodiment differs in that the ratio of raw materials in the S2 mixed solution is changed, and the specific implementation steps are as follows:

[0039] S2, 0.3g ammonium persulfate, 20g sodium dodecyl sulfate and 100g deionized water were mixed evenly, and stirred at 80°C for 2h to obtain a dispersion; 10g modified silica nanoparticles, 12g alumina nanoparticles and 100g acetic acid and ethanol in a volume ratio of 1:1 were mixed, ultrasonicated, and 1g chitosan was added and stirred to obtain a mixed solution; the dispersion and the mixed solution were mixed, and heating and stirring were continued to obtain a prepolymer; ammonium persulfate was added to the prepolymer and stirred evenly, and the amount of initiator added was 1.5% of the weight of the prepolymer, centrifuged, washed, and dried to obtain a modified silica nanoparticle / alumina polymer;

[0040] The remaining raw materials and preparation process remain the same as in Example 1.

[0041] Example 4

[0042] Compared with Example 1, this embodiment differs in that the ratio of the raw materials in the S2 dispersion and the mixed solution is changed at the same time, and the specific implementation steps are as follows:

[0043] S2, 0.4g ammonium persulfate, 19g sodium dodecyl sulfate and 100g deionized water were mixed evenly, and stirred at 80°C for 2h to obtain a dispersion; 8g modified silica nanoparticles, 15g alumina nanoparticles and 100g acetic acid and ethanol in a volume ratio of 1:1 were mixed, ultrasonicated, and 2g chitosan was added and stirred to obtain a mixed solution; the dispersion and the mixed solution were mixed, and heating and stirring were continued to obtain a prepolymer; ammonium persulfate was added to the prepolymer and stirred evenly, and the amount of initiator added was 1.5% of the weight of the prepolymer, centrifuged, washed, and dried to obtain a modified silica nanoparticle / alumina polymer;

[0044] The remaining raw materials and preparation process remain the same as in Example 1.

[0045] Example 5

[0046] Compared with Example 1, the difference between this example and Example 1 is that "8g of silicon dioxide nanoparticles, 1.5g of 3-(methacryloyloxy)propyltrimethoxysilane" in S1 is changed to "10g of silicon dioxide nanoparticles, 1g of 3-(methacryloyloxy)propyltrimethoxysilane", and the specific implementation steps are as follows:

[0047] S1. Mix 10 g of silica nanoparticles, 1 g of 3-(methacryloyloxy)propyltrimethoxysilane and 40 mL of deionized water, adjust the pH to 4, stir in a 60°C water bath for 4 h, wash three times with a 1:1 ether-acetone mixture, centrifuge at a speed of 10,000 r / min, dialyze with a dialysis bag with a molecular weight cutoff of 10,000 for 5 days, and replace the deionized water every day to obtain modified silica nanoparticles;

[0048] The remaining raw materials and preparation process remain the same as in Example 1.

[0049] Example 6

[0050] Compared with Example 1, this example is different in that "3-(methacryloyloxy)propyltrimethoxysilane" is replaced with "2-(carboxymethylthio)ethyltrimethylsilane". The specific implementation steps are as follows:

[0051] S1. 8 g of silica nanoparticles, 1.5 g of 2-(carboxymethylthio)ethyltrimethylsilane and 40 mL of deionized water were mixed, the pH was adjusted to 4, stirred in a 60° C. water bath for 4 h, washed three times with a 1:1 ether-acetone mixture, centrifuged at a speed of 10,000 r / min, dialyzed with a dialysis bag with a molecular weight cutoff of 10,000 for 5 days, and the deionized water was replaced every day to obtain modified silica nanoparticles;

[0052] The remaining raw materials and preparation process remain the same as in Example 1.

[0053] Example 7

[0054] Compared with Example 1, this example is different in that "3-(methacryloyloxy)propyltrimethoxysilane" is replaced with "monoethoxysilane-PEG-carboxylic acid". The specific implementation steps are as follows:

[0055] S1. 8 g of silica nanoparticles, 1.5 g of monoethoxysilane-PEG-carboxylic acid and 40 mL of deionized water were mixed, the pH was adjusted to 4, stirred in a 60 °C water bath for 4 h, washed three times with a 1:1 ether-acetone mixture, centrifuged at a speed of 10,000 r / min, dialyzed with a dialysis bag with a molecular weight cutoff of 10,000 for 5 days, and the deionized water was replaced every day to obtain modified silica nanoparticles;

[0056] The remaining raw materials and preparation process remain the same as in Example 1.

[0057] Comparative Example 1

[0058] Compared with Example 1, this comparative example differs in that no silane coupling agent is added, and the specific implementation steps are as follows:

[0059] S1. Mix 0.3g of ammonium persulfate, 20g of sodium dodecyl sulfate and 100g of deionized water, stir at 80°C for 2h to obtain a dispersion; mix 9g of silica nanoparticles, 15g of alumina nanoparticles and 100g of acetic acid and ethanol in a volume ratio of 1:1, ultrasonicate, add 1.5g of chitosan and stir to obtain a mixed solution; mix the dispersion and the mixed solution, continue heating and stirring to obtain a prepolymer; add ammonium persulfate to the prepolymer and stir evenly, add an initiator in an amount of 1.5% of the weight of the prepolymer, centrifuge, wash, and dry to obtain a modified silica nanoparticle / alumina polymer;

[0060] S3. In an inert gas atmosphere, a functional film is formed on the surface of a pretreated substrate by a magnetron coating method using modified silicon dioxide nanoparticles / aluminum oxide polymers. The thickness of the functional film is 60 μm.

[0061] The remaining raw materials and preparation process remain the same as in Example 1.

[0062] Comparative Example 2

[0063] Compared with Example 1, this comparative example differs in that no modified silicon dioxide nanoparticles are added, and the specific implementation steps are as follows:

[0064] S1. Mix 0.3g of ammonium persulfate, 20g of sodium dodecyl sulfate and 100g of deionized water, stir at 80°C for 2h to obtain a dispersion; mix 24g of aluminum oxide nanoparticles and 100g of acetic acid and ethanol in a volume ratio of 1:1, ultrasonicate, add 1.5g of chitosan and stir to obtain a mixed solution; mix the dispersion and the mixed solution, continue heating and stirring to obtain a prepolymer; add ammonium persulfate to the prepolymer and stir evenly, add an initiator in an amount of 1.5% of the weight of the prepolymer, centrifuge, wash, and dry to obtain a modified silica nanoparticle / alumina polymer;

[0065] S2. In an inert gas atmosphere, a functional film is formed on the surface of a pretreated substrate by a magnetron coating method using modified silicon dioxide nanoparticles / aluminum oxide polymers. The thickness of the functional film is 60 μm.

[0066] The remaining raw materials and preparation process remain the same as in Example 1.

[0067] Comparative Example 3

[0068] Compared with Example 1, this comparative example differs in that no initiator is added, and the specific implementation steps are as follows:

[0069] S2, 0.3g ammonium persulfate, 20g sodium dodecyl sulfate and 100g deionized water were mixed evenly, and stirred at 80°C for 2h to obtain a dispersion; 9g modified silica nanoparticles, 15g alumina nanoparticles and 100g acetic acid and ethanol in a volume ratio of 1:1 were mixed, ultrasonicated, 1.5g chitosan was added and stirred to obtain a mixed solution; the dispersion and the mixed solution were mixed, heated and stirred continuously, centrifuged, washed, and dried to obtain a modified silica nanoparticle / alumina polymer;

[0070] The remaining raw materials and preparation process remain the same as in Example 1.

[0071] Comparative Example 4

[0072] Compared with Example 1, this comparative example differs in that modified silicon dioxide and aluminum oxide nanoparticles are not added, and the specific implementation steps are as follows:

[0073] S1. Mix 0.3 g of ammonium persulfate, 20 g of sodium dodecyl sulfate and 100 g of deionized water, stir at 80° C. for 2 h to obtain a dispersion; mix 124 g of acetic acid and ethanol in a volume ratio of 1:1, ultrasonicate, add 1.5 g of chitosan and stir to obtain a mixed solution; mix the dispersion and the mixed solution, continue heating and stirring to obtain a prepolymer; add ammonium persulfate to the prepolymer and stir evenly, add an initiator in an amount of 1.5% of the weight of the prepolymer, centrifuge, wash, and dry to obtain a modified silica nanoparticle / alumina polymer;

[0074] S2. In an inert gas atmosphere, a functional film is formed on the surface of a pretreated substrate by a magnetron coating method using modified silicon dioxide nanoparticles / aluminum oxide polymers. The thickness of the functional film is 60 μm.

[0075] The remaining raw materials and preparation process remain the same as in Example 1.

[0076] The performance tests were performed on Examples 1 to 7 and Comparative Examples 1 to 4.

[0077] According to HG / T 4303-2012, the functional films obtained in various embodiments and comparative examples of the present application were subjected to a wear resistance test (5000 frictions with a load of 500 g);

[0078] According to GB / T 2410-2008, the functional films obtained in various embodiments and comparative examples of the present application were tested for light transmittance;

[0079] According to GB / T 2680-2021, the functional films obtained in various embodiments and comparative examples of the present application were tested for UV blocking rate;

[0080] The results are shown in Table 1:

[0081] Table 1

[0082]

[0083]

[0084] According to the set examples, comparative examples and the data in Table 1, it can be seen that the difference between Examples 2-7 and Example 1 lies in the raw material ratio and the change of the raw materials within a reasonable range. From the test data, the prepared film has good wear resistance, light transmittance and strong shielding against ultraviolet light. In addition, we found that the use of a silane coupling agent containing a carboxyl group can improve the performance of the film more, because the carboxyl group can combine with alumina, enhance the chemical bonding between nano-silica and alumina, and thus improve the performance of the film.

[0085] Compared with Example 1, in Comparative Example 1, after not adding silane coupling agent, the dispersibility of nano-silica and the bonding effect with alumina nanoparticles become worse, thereby reducing the overall performance of the film; compared with Example 1, in Comparative Example 2, on the basis of Comparative Example 1, no silica nanoparticles are added, so that the wear resistance and UV protection performance of the film are greatly reduced; compared with Example 1, the difference between Comparative Example 3 and Example 1 lies in the optimization of the process, and the additional addition of an initiator after mixing the dispersion and the mixed liquid helps the modified silica nanoparticles / alumina polymer to better bond and form a film, thereby improving the film performance; in Comparative Example 4, in combination with Comparative Examples 1-2, compared with Example 1, since alumina has higher hardness and wear resistance, it not only further improves the wear resistance of the film, but also improves the dispersibility of the nano-silica through electrostatic adsorption with the modified silica nanoparticles, thereby playing a complementary role.

[0086] In summary, the present invention provides a glass surface functional film and its preparation and application. The prepared film has good wear resistance, light transmittance and ultraviolet blocking rate, and its application in LOW-E glass has good application prospects.

[0087] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0088] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a functional film on a glass surface, characterized in that: The following steps are involved: S1. Mix ammonium persulfate, sodium dodecyl sulfate and deionized water uniformly, heat and stir to obtain a dispersion; mix modified silica nanoparticles, alumina nanoparticles and a solvent, ultrasonicate, add chitosan and stir to obtain a mixed solution; mix the dispersion and the mixed solution, continue heating and stirring to obtain a prepolymer; add an initiator to the prepolymer and stir uniformly, centrifuge, wash and dry to obtain a modified silica nanoparticle / alumina polymer; S2. In an inert gas atmosphere, the modified silica nanoparticles / alumina polymer is coated on the pretreated substrate surface by magnetron coating to form a functional film.

2. The method for preparing a glass surface functional film according to claim 1, characterized in that: The modified silicon dioxide nanoparticles are prepared by the following steps: The silicon dioxide nanoparticles, the silane coupling agent and the deionized water are mixed, the pH value is adjusted, the mixture is heated and stirred, and the mixture is washed and dialyzed to obtain the modified silicon dioxide nanoparticles.

3. The method for preparing a glass surface functional film according to claim 2, characterized in that: The dosage ratio of the silicon dioxide nanoparticles, the silane coupling agent and the deionized water is (6-10) g: (1-1.5) g: (35-40) mL; and the pH is adjusted to 3-4.

4. The method for preparing a glass surface functional film according to claim 2, characterized in that: The silane coupling agent is one or a combination of 3-(methacryloyloxy)propyltrimethoxysilane, monoethoxysilane-PEG-carboxylic acid and 2-(carboxymethylthio)ethyltrimethylsilane.

5. The method for preparing a glass surface functional film according to claim 1, characterized in that: The usage ratio of ammonium persulfate, sodium dodecyl sulfate and deionized water in the dispersion is (0.2-0.4) g: (15-25) g: (80-120) g.

6. The method for preparing a glass surface functional film according to claim 1, characterized in that: The dosage ratio of modified silicon dioxide nanoparticles, aluminum oxide nanoparticles, solvent and chitosan in the mixed solution is (8-10) g: (12-15) g: (80-100) g: (1-2) g.

7. The method for preparing a glass surface functional film according to claim 1, characterized in that: The solvent is a mixture of acetic acid and ethanol in a volume ratio of 1:1; the heating and stirring is stirring at 60-80° C. for 2-4 hours; the initiator is ammonium persulfate, and the added amount of the initiator is 1% to 2% of the weight of the prepolymer.

8. The method for preparing a glass surface functional film according to claim 1, characterized in that: The surface of the pretreated substrate is clean and pollution-free; the thickness of the film is 50-70 μm.

9. A glass surface functional film, characterized in that: The glass surface functional film is prepared by the method for preparing a glass surface functional film according to any one of claims 1 to 8.

10. Use of the glass surface functional film according to any one of claims 1 to 9 in Low-E glass.

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