Anti-reflective, Anti-bacterial and Anti-fouling coating and preparation method therefor

Abstract

The present invention relates to the technical field of coating compositions, and in particular to an anti-reflective, anti-bacterial and anti-fouling coating and a preparation method therefor. The preparation method comprises the following steps: applying an inorganic nanosol to the surface of a base material, drying the base material, and then placing the base material at a first set temperature for calcination to prepare an anti-reflective coating on the surface of the base material; placing the anti-reflective coating in an ammonium salt solution having a first set concentration for a first set time, then using a second solvent to rinse the anti-reflective coating, and then drying the anti-reflective coating to prepare an anti-bacterial coating on the surface of the anti-reflective coating; and placing the anti-bacterial coating in a fluorosilane solution having a second set concentration for a second set time, then using a third solvent to rinse the anti-bacterial coating, and then drying the anti-bacterial coating to form an anti-fouling coating on the surface of the anti-bacterial coating. The anti-reflective, anti-bacterial and anti-fouling coating and the preparation method therefor provided by the present invention solve the problem of an anti-reflective coating being easily contaminated by bacteria and oil stains, so that the anti-reflective, anti-bacterial and anti-fouling coating has anti-reflection, anti-bacterial and anti-fouling functions.

Description

An anti-reflective, antibacterial, and anti-fouling coating and its preparation method Technical Field

[0001] This invention relates to the field of coating composition technology, and in particular to an anti-reflective, antibacterial, and anti-fouling coating and its preparation method. Background Technology

[0002] With the rapid development of science and technology, the application of visual screens is becoming increasingly widespread, including portable electronic devices, self-service office supplies, and medical devices. However, frequent use of interactive screens makes them a medium for the transmission of pathogenic microorganisms between people. These microorganisms can also be transmitted from hands to the environment, causing many infectious diseases. Disinfecting touchscreens with chemical disinfectants is very difficult. Alcohol and other components in disinfectants risk damaging the coating. Antibacterial technologies can effectively reduce the growth and spread of microorganisms on touchscreen surfaces, but related research is very limited. Furthermore, excessive reflection from the touchscreen surface negatively impacts the user experience; therefore, coatings applied to interactive screens need to have a certain degree of anti-reflective capability. SiO2 has advantages such as good biocompatibility and low refractive index, making it an ideal material for preparing antireflective coatings. Therefore, developing SiO2 coatings with antibacterial properties is of great significance for their application on touchscreens.

[0003] A promising recent strategy is to integrate antibacterial metal nanoparticles (NPs), such as Ag-NPs, Cu-NPs, and Zn-NPs, into coatings. Metal NPs primarily kill bacteria by releasing metal ions that disrupt bacterial metabolism. However, with prolonged use, metal NPs continuously hydrolyze and migrate to the coating surface, leading to a gradual decline in the coating's antibacterial properties.

[0004] Grafting small molecules with bactericidal properties onto coating surfaces via surface chemical engineering is a promising alternative method. QAS-functionalized polymers are widely used to construct contact sterilization systems for textiles due to their effective antibacterial properties. However, QAS-functionalized surfaces are prone to hygroscopicity, attracting water containing bacteria to adhere to their surfaces, thus forming biofilms and reducing antibacterial efficiency. Low-energy hydrophobic surfaces can effectively inhibit bacterial adhesion but cannot inhibit bacterial reproduction. Furthermore, frequent finger touches leave grease on screens, increasing the risk of bacterial transmission. Therefore, research into antibacterial and anti-fouling (dual-anti-reflective) coatings is urgently needed. Summary of the Invention

[0005] The present invention aims to at least solve one of the technical problems existing in the related art. To this end, the present invention provides an anti-reflective, antibacterial, and anti-fouling coating and its preparation method, which solves the problem that anti-reflective coatings are easily contaminated by bacteria and oil stains, and enables it to have anti-reflective, antibacterial, and anti-fouling functions.

[0006] This invention provides a method for preparing an anti-reflective, antibacterial, and anti-fouling coating, comprising the following steps:

[0007] Silane is added to the first solvent, and under the catalysis of an acid catalyst or an alkaline catalyst, it is stirred and hydrolyzed at 15℃~30℃ for 0.5h~24h and then aged for more than 24h to obtain an acid-catalyzed inorganic nanosol or an alkaline-catalyzed inorganic nanosol. The prepared acid-catalyzed inorganic nanosol and alkaline-catalyzed inorganic nanosol are uniformly mixed in a set ratio to obtain the final inorganic nanosol.

[0008] S2: The inorganic nanosol is coated onto the surface of the substrate, dried at 15℃~30℃, and then calcined at a first set temperature to prepare an anti-reflective coating on the surface of the substrate.

[0009] S3: The anti-reflective coating is placed in an ammonium salt solution of a first set concentration for a first set time, then rinsed and dried to prepare an antibacterial coating on the surface of the anti-reflective coating;

[0010] S4: The antibacterial coating is placed in a fluorosilane solution of a second set concentration for a second set time, then rinsed and dried to form an anti-fouling coating on the surface of the antibacterial coating.

[0011] A further improvement of the preparation method of the anti-reflective, antibacterial and anti-fouling coating of the present invention is that the silane is tetraethyl orthosilicate and the first solvent is ethanol or isopropanol.

[0012] A further improvement of the preparation method of the anti-reflective, antibacterial and anti-fouling coating of the present invention is that the acid catalyst is any one of hydrochloric acid, acetic acid or phosphoric acid, and the alkaline catalyst is any one of sodium hydroxide, potassium hydroxide or ammonia water with a mass fraction of 25% to 44%.

[0013] A further improvement to the preparation method of the anti-reflective, antibacterial, and anti-fouling coating of the present invention lies in that the mass ratio of each substance in the acid-catalyzed inorganic nano-sol is silane: first solvent: acid catalyst = (0-10):(0-10):(0.1-5), and the mass ratio of each substance in the alkali-catalyzed inorganic nano-sol is silane: first solvent: alkali catalyst = (0-10):(0-10):(0.1-5), and the final inorganic nano-sol has a mass ratio of acid-catalyzed inorganic nano-sol to alkali-catalyzed inorganic nano-sol of 1:

[0014] (0~10).

[0015] A further improvement of the preparation method of the anti-reflective, antibacterial and anti-fouling coating of the present invention is that the coating method when the inorganic nano-sol is coated on the substrate surface is any one of the following: dip coating, roller coating, spray coating and spin coating.

[0016] A further improvement of the preparation method of the anti-reflective, antibacterial and anti-fouling coating of the present invention is that the first set concentration is 0.5% to 10% by mass, the solute in the ammonium salt solution is any one of octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, N,N-dimethyl-N-octadecylaminopropyltrimethoxysilane ammonium salt or dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, and the solvent in the ammonium salt solution is any one of ethanol, isopropanol or n-butanol.

[0017] A further improvement to the preparation method of the anti-reflective, antibacterial, and anti-fouling coating of the present invention is that ethanol is used for rinsing in step S3.

[0018] A further improvement of the preparation method of the anti-reflective, antibacterial and anti-fouling coating of the present invention is that the second set concentration is 0.2% to 5% by mass, the solute in the fluorosilane solution is any one of heptadecafluorodecyltriethoxysilane and tridecafluorooctyltriethoxysilane, and the solvent in the fluorosilane solution is any one of methyl nonafluorobutyl ether or ethanol.

[0019] A further improvement to the preparation method of the anti-reflective, antibacterial, and anti-fouling coating of the present invention is that ethanol is used for rinsing in step S4.

[0020] An antireflective, antibacterial, and antifouling coating is prepared using the preparation method described above. The antireflective, antibacterial, and antifouling coating is formed on the surface of a substrate. The antireflective, antibacterial, and antifouling coating includes an antireflective coating, an antibacterial coating, and an antifouling coating formed sequentially.

[0021] The above-described one or more technical solutions in the embodiments of the present invention have at least one of the following technical effects:

[0022] (1) The coating prepared by the present invention has excellent anti-reflection properties and an average light transmittance of more than 93.4%. The molecular chains entangled between inorganic nanomaterials give it a dense continuous structure and ultra-low surface roughness, providing a platform for subsequent interface modification.

[0023] (2) Ammonium salts are grafted onto the coating surface in the form of covalent bonds. The "N+" on the molecular chain improves the antibacterial effect of the coating and has an antibacterial efficiency of more than 80% against various bacteria such as Escherichia coli and Staphylococcus aureus.

[0024] (3) Post-modification with fluorosilane further improves the antibacterial properties of the coating, with an antibacterial efficiency of over 99.9% against various bacteria such as Escherichia coli and Staphylococcus aureus.

[0025] (4) The coating prepared by the present invention has excellent anti-pollution properties. The grease on the coating surface cannot spread, and water droplets can slide off at a low tilt angle.

[0026] (5) The coating prepared by the present invention has excellent mechanical durability and can maintain long-lasting antibacterial, anti-fouling and anti-reflective properties and transparency enhancement effect.

[0027] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0029] Figure 1 is a flowchart of a method for preparing an anti-reflective, antibacterial, and anti-fouling coating according to the present invention.

[0030] Figure 2 shows a scanning electron microscope (SEM) image of the anti-reflective coating obtained in Example 1.

[0031] Figure 3 shows a scanning electron microscope (SEM) image of the anti-reflective and antibacterial coating obtained in Example 1.

[0032] Figure 4 shows a scanning electron microscope (SEM) image of the anti-reflective, antibacterial, and anti-fouling coating obtained in Example 1.

[0033] Figure 5 shows the FTIR spectrum of the anti-reflective, antibacterial, and anti-fouling coating obtained in Example 1.

[0034] Figure 6 shows the XPS spectrum of the anti-reflective, antibacterial, and anti-fouling coating obtained in Example 1.

[0035] Figure 7 shows the high-magnification XPS spectrum of N in the anti-reflective, antibacterial, and anti-fouling coating obtained in Example 1.

[0036] Figure 8 shows a scanning electron microscope (SEM) image of the antireflective coating obtained in Comparative Example 1.

[0037] Figure 9 shows a scanning electron microscope (SEM) image of the anti-reflective and anti-fouling coating obtained in Comparative Example 1.

[0038] Figure 10 shows a scanning electron microscope (SEM) image of the anti-reflective, anti-fouling, and antibacterial coating obtained in Comparative Example 1. Detailed Implementation

[0039] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention. The following embodiments are used to illustrate this invention but should not be used to limit the scope of this invention.

[0040] Please refer to Figure 1. The following describes a method for preparing an anti-reflective, antibacterial, and anti-fouling coating according to the present invention, comprising the following steps:

[0041] S1: Silane is added to the first solvent, and under the catalysis of an acid catalyst or an alkaline catalyst, it is stirred and hydrolyzed at 15℃~30℃ for 0.5h~24h, and then aged for more than 24h to obtain an acid-catalyzed inorganic nanosol or an alkaline-catalyzed inorganic nanosol; the prepared acid-catalyzed inorganic nanosol and alkaline-catalyzed inorganic nanosol are uniformly mixed in a set ratio to obtain the final inorganic nanosol; the mass ratio of each substance in the acid-catalyzed inorganic nanosol is silane: first solvent: acid catalyst = (0~10): (0~10): (0.1~5), the mass ratio of each substance in the alkaline-catalyzed inorganic nanosol is silane: first solvent: alkaline catalyst = (0~10): (0~10): (0.1~5), and the mass ratio of acid-catalyzed inorganic nanosol and alkaline-catalyzed inorganic nanosol in the final inorganic nanosol is 1: (0~10);

[0042] S2: The inorganic nanosol is coated onto the surface of the substrate, dried at 15℃~30℃, and then calcined at the first set temperature to prepare an anti-reflective coating on the surface of the substrate.

[0043] S3: The anti-reflective coating is placed in an ammonium salt solution of a first set concentration for a first set time, and then rinsed with a second solvent and dried to prepare an antibacterial coating on the surface of the anti-reflective coating;

[0044] S4: The antibacterial coating is placed in a fluorosilane solution of a second set concentration for a second set time, and then rinsed with a third solvent and dried to form an anti-fouling coating on the surface of the antibacterial coating.

[0045] Specifically, the silane is tetraethyl orthosilicate.

[0046] In another specific implementation, an inorganic nano-titanium dioxide antireflective coating can be formed on a substrate, and then an ammonium salt antibacterial coating can be grafted onto the titanium dioxide antireflective coating. This inorganic nano-titanium dioxide antireflective coating is formed using a sol-gel method. The inorganic nano-sol is prepared using tetrabutyl titanate or titanium dioxide as raw materials.

[0047] It should be noted that the mass ratio of acid-catalyzed inorganic nanosol and alkali-catalyzed inorganic nanosol in the final inorganic nanosol can be selected as 1:9, 1:5, 1:4, 1:2.5, 1:2, 1:1, etc.

[0048] Specifically, the first solvent is ethanol or isopropanol.

[0049] Specifically, the acid catalyst is one of hydrochloric acid, acetic acid, or phosphoric acid, and the base catalyst is any one of sodium hydroxide, potassium hydroxide, or ammonia water with a mass fraction of 25% to 44%.

[0050] It should be noted that the mass fraction of ammonia water can be selected as 25%, 30%, 35%, 40%, 42%, and 44%.

[0051] Preferably, the ammonia water has a mass fraction of 25%.

[0052] Specifically, the coating method for applying inorganic nano-sol to the substrate surface is any one of the following: dip coating, roller coating, spray coating, or spin coating.

[0053] It should be noted that the first set temperature can also be selected as 100℃, 105℃, 110℃, 115℃, or 120℃.

[0054] Preferably, the first set temperature is 120°C.

[0055] Specifically, the first set concentration is 0.5% to 10% by mass, the solute in the ammonium salt solution is any one of octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, N,N-dimethyl-N-octadecylaminopropyltrimethoxysilane ammonium salt or dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, and the solvent in the ammonium salt solution is any one of ethanol, isopropanol or n-butanol.

[0056] It should be noted that the first set concentration can be selected as 2%, 3%, 4%, or 5%.

[0057] Preferably, the first set concentration can be selected as 5%.

[0058] It should be noted that the first set time can be 20h, 24h, 28h, 30h, 35h, or 40h.

[0059] Preferably, the first set time is 24 hours, and the second solvent is ethanol; the operation method after rinsing with the second solvent and drying is to rinse three times with ethanol and dry in an oven at 115°C for 1 hour.

[0060] Specifically, the second set concentration is 0.2% to 5% by mass, the solute in the fluorosilane solution is either heptadecafluorodecyltriethoxysilane or tridecafluorooctyltriethoxysilane, and the solvent in the fluorosilane solution is either methyl nonafluorobutyl ether (Novec 7100) or ethanol.

[0061] It should be noted that those skilled in the art can choose a second set concentration of 3%, 4%, 5%, etc. by mass fraction, and the present invention does not impose specific restrictions on the value of the second set concentration.

[0062] It should be noted that the second set time can be 0.5h, 1h, 1.5h, 2h, 2.5h, or 3h.

[0063] Preferably, the second set time is 1 hour, and the third solvent is ethanol; the operation method after rinsing with the third solvent and drying is to rinse three times with ethanol and then place it in an oven at 120°C to dry for 1 hour.

[0064] The present invention also provides an anti-reflective, antibacterial and anti-fouling coating, which is prepared by the above preparation method. The anti-reflective, antibacterial and anti-fouling coating is formed on the surface of the substrate. The anti-reflective, antibacterial and anti-fouling coating includes an anti-reflective coating, an antibacterial coating and an anti-fouling coating formed sequentially.

[0065] The above-described one or more technical solutions in the embodiments of the present invention have at least one of the following technical effects:

[0066] (1) The coating prepared by the present invention has excellent anti-reflection properties and an average light transmittance of more than 93.4%. The molecular chains entangled between inorganic nanomaterials give it a dense continuous structure and ultra-low surface roughness, providing a platform for subsequent interface modification.

[0067] (2) Ammonium salts are grafted onto the coating surface in the form of covalent bonds. The "N+" on the molecular chain improves the antibacterial effect of the coating and has an antibacterial efficiency of more than 80% against various bacteria such as Escherichia coli and Staphylococcus aureus.

[0068] (3) Post-modification with fluorosilane further improves the antibacterial properties of the coating, with an antibacterial efficiency of over 99.9% against various bacteria such as Escherichia coli and Staphylococcus aureus.

[0069] (4) The coating prepared by the present invention has excellent anti-pollution properties. The grease on the coating surface cannot spread, and water droplets can slide off at a low tilt angle.

[0070] (5) The coating prepared by the present invention has excellent mechanical durability and can maintain long-lasting antibacterial, anti-fouling and anti-reflective properties and transparency enhancement effect.

[0071] The preparation method and characterization results of the anti-reflective, antibacterial and anti-fouling coating of the present invention will be described below with reference to specific implementation cases.

[0072] Example 1

[0073] S1: Add 5g of tetraethyl orthosilicate to 35.5g of ethanol and stir for 15min. Add 1.8g of deionized water and 0.5g of hydrochloric acid (12mol / L) and continue stirring for 1h. Finally, let it stand for 7 days to obtain inorganic nanosol of silica.

[0074] S2: Immerse a completely clean glass plate into the inorganic nano-sol of silica, then pull it up at a uniform speed, dry it at room temperature for 10 minutes, pre-cur it in an oven at 120°C for 1 hour, and sinter it at 300°C for 1 hour to make an anti-reflective coating of silica.

[0075] S3: Add 2g of octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride to 98g of ethanol to prepare an antibacterial modification solution with a mass fraction of 2%; place the above antireflective coating in the antibacterial modification solution and react for 24h, rinse 3 times with ethanol, and then place it in an oven at 115℃ for 1h to prepare an antibacterial coating.

[0076] S4: The above anti-reflective and antibacterial coating is placed in a 0.3% heptadecafluorodecyltriethoxysilane solution for 1 hour (solvent is Novec 7100), then rinsed with ethanol 3 times and placed in an oven at 120°C for 1 hour to prepare an anti-reflective, antibacterial and anti-fouling coating.

[0077] The anti-reflective, antibacterial, and anti-fouling coating obtained in Example 1 was characterized by the following testing equipment: ultraviolet spectrophotometer, biochemical incubator, and plate counter.

[0078] As can be seen from Figure 2, the surface of the antireflective coating prepared in step S2 is very dense and flat.

[0079] As can be seen from Figure 3, the surface of the anti-reflective coating obtained by step S3 after the ammonium salt is used to form an anti-reflective and antibacterial coating is very dense and flat.

[0080] As can be seen from Figure 4, the surface of the anti-reflective, antibacterial, and anti-fouling coating prepared in step S4 is very dense and flat.

[0081] As shown in Figure 5, the antireflective and antibacterial coating prepared in Example 1 is effective at 2990 cm⁻¹. -1 The stretching vibration peak (CH) of ammonium salt was observed at the surface, while the peak was not detected on silicon dioxide, indicating that the ammonium salt was successfully grafted onto the surface of the antireflective coating of silicon dioxide.

[0082] Figure 6 shows the XPS spectrum of the anti-reflective, antibacterial, and anti-fouling coating. Seven elemental characteristic peaks were detected, namely Si2p, Si2s, C1s, N1s, N+1s, O1s, and F1s.

[0083] Figure 7 shows the high-magnification XPS spectrum of N in the anti-reflective, antibacterial, and antifouling coating, indicating that the antibacterial coating structure is intact and that preparing an antifouling coating on the antibacterial coating will not affect the integrity of the antibacterial coating.

[0084] Comparative Example 1

[0085] S1: Add 5g of tetraethyl orthosilicate to 35.5g of ethanol and stir for 15min. Add 1.8g of deionized water and 0.5g of hydrochloric acid (12mol / L) and continue stirring for 1h. Finally, let it stand for 7 days to obtain inorganic nanosol of silica.

[0086] S2: Immerse a completely clean glass plate into the inorganic nano-sol of silica, then pull it up at a uniform speed, dry it at room temperature for 10 minutes, pre-cur it in an oven at 120°C for 1 hour, and sinter it at 300°C for 1 hour to make an anti-reflective coating of silica.

[0087] S3: The above anti-reflective coating is placed in a 0.3% heptadecafluorodecyltriethoxysilane solution for 1 hour (solvent is Novec 7100), then rinsed 3 times with ethanol and placed in an oven at 120°C for 1 hour to prepare an anti-reflective and anti-fouling coating.

[0088] S4: Add 2g of octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride to 98g of ethanol to prepare a 2% (w / w) antibacterial modification solution; place the above antireflective coating in the antibacterial modification solution and react for 24h, rinse 3 times with ethanol, and then place it in an oven at 115℃ for 1h to prepare an antireflective, anti-fouling, and antibacterial coating.

[0089] The main difference between Comparative Example 1 and Example 1 is the adjustment of the preparation order of the antibacterial coating and the antifouling coating. The antireflective, antifouling and antibacterial coating prepared in Comparative Example 1 was characterized by the following tests: Figures 8, 9 and 10 show that the surfaces of the antireflective coating, the antireflective and antifouling coating and the antireflective, antifouling and antibacterial coating are very dense.

[0090] Example 2

[0091] S1: Add 5g of tetraethyl orthosilicate to 35.5g of ethanol and stir for 15min. Add 1.8g of deionized water and 0.5g of hydrochloric acid (12mol / L) and continue stirring for 1h. Finally, let it stand for 7 days to obtain inorganic nanosol of silica.

[0092] S2: Immerse a completely clean glass plate into the inorganic nano-sol of silica, then pull it up at a uniform speed, dry it at room temperature for 10 minutes, pre-cur it in an oven at 120°C for 1 hour, and sinter it at 300°C for 1 hour to make an anti-reflective coating of silica.

[0093] S3: 10g of N,N-dimethyl-N-octadecylaminopropyltrimethoxysilane ammonium salt was added to 90g of isopropanol to prepare a 10% (w / w) antibacterial modification solution. The above-mentioned silica antireflective coating was placed in this antibacterial modification solution and reacted for 24h. After rinsing three times with ethanol, it was placed in a 120℃ oven for 1h to prepare the antibacterial coating.

[0094] S4: The above anti-reflective and antibacterial coating is placed in a 0.8% heptadecafluorodecyltriethoxysilane solution for 1 hour (solvent is Novec 7100), then rinsed with ethanol 3 times and placed in an oven at 120°C for 1 hour to prepare an anti-reflective, antibacterial and anti-fouling coating.

[0095] Example 3

[0096] S1: Add 5g of tetraethyl orthosilicate to 35.5g of ethanol and stir for 15min. Add 1.8g of deionized water and 0.5g of hydrochloric acid (12mol / L) and continue stirring for 1h. Finally, let it stand for 7 days to obtain inorganic nanosol of silica.

[0097] S2: Immerse a completely clean glass plate into the inorganic nano-sol of silica, then pull it up at a uniform speed, dry it at room temperature for 10 minutes, pre-cur it in an oven at 120°C for 1 hour, and sinter it at 300°C for 1 hour to make an anti-reflective coating of silica.

[0098] S3: 2.5 g of N,N-dimethyl-N-octadecylaminopropyltrimethoxysilane ammonium salt was added to 97.5 g of isopropanol to prepare a 2.5% (w / w) antibacterial modification solution. The above-mentioned silica antireflective coating was placed in this antibacterial modification solution and reacted for 24 h. After rinsing three times with ethanol, it was placed in an oven at 115 °C for 1 h to prepare the antibacterial coating.

[0099] S4: Place the above anti-reflective and antibacterial coating in a 1% tridecafluorooctyltriethoxysilane solution for 1 hour (solvent is Novec 7100), then rinse with ethanol 3 times and place in a 120°C oven for 1 hour to prepare an anti-reflective, antibacterial and anti-fouling coating.

[0100] Example 4

[0101] S1: Add 3g of tetraethyl orthosilicate to 40.5g of ethanol and stir for 15min. Add 1g of deionized water and 0.5g of hydrochloric acid (12mol / L) and continue stirring for 1h. Finally, inorganic nanosol of silica is obtained after 7 days.

[0102] S2: Immerse a completely clean glass plate into the inorganic nano-sol of silica, then pull it up at a uniform speed, dry it at room temperature for 10 minutes, pre-cur it in an oven at 120°C for 1 hour, and sinter it at 300°C for 1 hour to make an anti-reflective coating of silica.

[0103] S3: Add 4g of octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride to 96g of ethanol to prepare a 4% (w / w) antibacterial modification solution. Place the above-mentioned silica antireflective coating in this antibacterial modification solution and react for 24h. After rinsing three times with ethanol, place it in an oven at 115℃ for 1h to prepare the antibacterial coating.

[0104] S4: Place the above anti-reflective and antibacterial coating in a 0.5% heptadecafluorodecyltriethoxysilane solution for 1 hour (solvent is ethanol), then rinse it three times with ethanol and place it in a 120°C oven for 1 hour to prepare an anti-reflective, antibacterial and anti-fouling coating.

[0105] Example 5

[0106] S1: Add 3g of tetraethyl orthosilicate to 40.5g of ethanol and stir for 15min. Add 1g of deionized water and 0.5g of hydrochloric acid (12mol / L) and continue stirring for 1h. Finally, inorganic nanosol of silica is obtained after 7 days.

[0107] S2: Immerse a completely clean glass plate into the inorganic nano-sol of silica, then pull it up at a uniform speed, dry it at room temperature for 10 minutes, pre-cur it in an oven at 120°C for 1 hour, and sinter it at 300°C for 1 hour to make an anti-reflective coating of silica.

[0108] S3: 2g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added to 98g of n-butanol to prepare a 2% (w / w) antibacterial modification solution. The above-mentioned silica antireflective coating was placed in this antibacterial modification solution and reacted for 24h. After rinsing three times with ethanol, it was placed in an oven at 115℃ for 1h to prepare the antibacterial coating.

[0109] S4: Place the above anti-reflective and antibacterial coating in a 0.8% heptadecafluorodecyltriethoxysilane solution for 1 hour (solvent is ethanol), then rinse it three times with ethanol and place it in a 120°C oven for 1 hour to prepare an anti-reflective, antibacterial and anti-fouling coating.

[0110] Example 6

[0111] S1: Add 3g of tetraethyl orthosilicate to 40.5g of isopropanol and stir for 15min. Add 1.5g of deionized water and 0.5g of acetic acid and continue stirring for 1h. Finally, inorganic nanosols containing silica are obtained after 7 days of aging.

[0112] S2: Immerse a completely clean glass plate into the inorganic nano-sol of silica, then pull it up at a uniform speed, dry it at room temperature for 10 minutes, pre-cur it in an oven at 120°C for 1 hour, and sinter it at 300°C for 1 hour to make an anti-reflective coating of silica.

[0113] S3: 2g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added to 98g of n-butanol to prepare a 2% (w / w) antibacterial modification solution. The above-mentioned silica antireflective coating was placed in this antibacterial modification solution and reacted for 24h. After rinsing three times with ethanol, it was placed in an oven at 115℃ for 1h to prepare the antibacterial coating.

[0114] S4: Place the above anti-reflective and antibacterial coating in a 0.5% heptadecafluorodecyltriethoxysilane solution for 1 hour (solvent is ethanol), then rinse it three times with ethanol and place it in a 120°C oven for 1 hour to prepare an anti-reflective, antibacterial and anti-fouling coating.

[0115] Compared to Example 1, although the acid catalyst and solvent conditions changed in Examples 2 to 6, the test results for whether the ammonium salt was grafted onto silica in the prepared antireflective, antibacterial, and antifouling coatings were the same as in Example 1, and will not be repeated here. Although the acid catalyst and solvent conditions changed in Examples 2 to 6, the surfaces of the prepared antireflective coatings were all very dense and flat (the characterization images were almost indistinguishable from those in Example 1), and exhibited good antireflective properties. The surfaces of the antibacterial coatings are all very dense and flat (characterization images are almost indistinguishable from those of Example 1), and the surfaces of the antireflective, antibacterial, and antifouling coatings are all very dense and flat (characterization images are almost indistinguishable from those of Example 1). Compared with Example 1, although the acid catalyst and solvent conditions are different in Examples 2 to 6, the FTIR spectra of the prepared antireflective, antibacterial, and antifouling coatings are almost indistinguishable from those of Example 1. The XPS spectra and high-magnification XPS spectra of the antireflective, antibacterial, and antifouling coatings of Examples 2 to 6 are the same as those of Example 1. The characterization results will not be described again in this application.

[0116] Example 7

[0117] S1: Add 7g of tetraethyl orthosilicate to 50g of ethanol and stir for 15min. Add 0.14g of ammonia and continue stirring for 1h. Finally, let it stand for 7 days to obtain an alkali-catalyzed inorganic nanosol. Add 3g of tetraethyl orthosilicate to 40.5g of ethanol and stir for 15min. Add 1.8g of deionized water and 0.3g of hydrochloric acid (12mol / L) and continue stirring for 1h. Finally, let it stand for 7 days to obtain an acid-catalyzed inorganic nanosol. Mix the acid-catalyzed inorganic nanosol and the alkali-catalyzed inorganic nanosol at a mass ratio of 2:8 to prepare the final inorganic nanosol.

[0118] S2: Preparation of anti-reflective coating: Immerse a completely clean glass plate in the sol, then pull it up at a uniform speed, dry it at room temperature for 10 minutes, pre-cur it in an oven at 120°C for 1 hour, and sinter it at 300°C for 1 hour to prepare a silicon dioxide anti-reflective coating.

[0119] S3: Preparation of antibacterial coating: 2g of octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride was added to 98g of ethanol to prepare a 2% (w / w) antibacterial modification solution. The above-mentioned silica antireflective coating was placed in this antibacterial modification solution and reacted for 24h. After rinsing three times with ethanol, it was placed in an oven at 115℃ for 1h to prepare the antibacterial coating.

[0120] S4: Preparation of anti-fouling coating: The above anti-reflective and antibacterial coating is placed in a 1% heptadecafluorodecyltriethoxysilane solution for 1 hour (solvent is ethanol), then rinsed 3 times with ethanol and placed in an oven at 120°C for 1 hour to prepare an anti-reflective, antibacterial and anti-fouling coating.

[0121] Example 8

[0122] S1: Add 5g of tetraethyl orthosilicate to 55g of ethanol and stir for 15min. Add 0.12g of ammonia and continue stirring for 1h. Finally, let it stand for 7 days to obtain an alkali-catalyzed inorganic nanosol. Add 5g of tetraethyl orthosilicate to 35.5g of ethanol and stir for 15min. Add 1.8g of deionized water and 0.3g of hydrochloric acid (12mol / L) and continue stirring for 1h. Finally, let it stand for 7 days to obtain an acid-catalyzed inorganic nanosol. Mix the acid-catalyzed inorganic nanosol and the alkali-catalyzed inorganic nanosol at a mass ratio of 3:7 to prepare the final inorganic nanosol.

[0123] S2: Preparation of anti-reflective coating: Immerse a completely clean glass plate in the sol, then pull it up at a uniform speed, dry it at room temperature for 10 minutes, pre-cur it in an oven at 120°C for 1 hour, and sinter it at 300°C for 1 hour to prepare a silicon dioxide anti-reflective coating.

[0124] S3: Preparation of antibacterial coating: 3g of octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride was added to 97g of ethanol to prepare a 3% (w / w) antibacterial modification solution. The above-mentioned silica antireflective coating was placed in this antibacterial modification solution and reacted for 24h. After rinsing three times with ethanol, it was placed in an oven at 115℃ for 1h to prepare the antibacterial coating.

[0125] S4: Preparation of anti-fouling coating: The above anti-reflective and antibacterial coating is placed in a 0.5% heptadecafluorodecyltriethoxysilane solution for 1 hour (solvent is ethanol), then rinsed 3 times with ethanol and placed in an oven at 120°C for 1 hour to prepare the anti-reflective, antibacterial and anti-fouling coating.

[0126] Example 9

[0127] S1: Add 5g of tetraethyl orthosilicate to 50g of ethanol and stir for 15min. Add 0.14g of ammonia and continue stirring for 1h. Finally, let it stand for 7 days to obtain an alkali-catalyzed inorganic nanosol. Add 4g of tetraethyl orthosilicate to 41g of ethanol and stir for 15min. Add 1.8g of deionized water and 0.3g of hydrochloric acid (12mol / L) and continue stirring for 1h. Finally, let it stand for 7 days to obtain an acid-catalyzed inorganic nanosol. Mix the acid-catalyzed inorganic nanosol and the alkali-catalyzed inorganic nanosol at a mass ratio of 1:9 to prepare the final inorganic nanosol.

[0128] S2: Preparation of anti-reflective coating: Immerse a completely clean glass plate in the sol, then pull it up at a uniform speed, dry it at room temperature for 10 minutes, pre-cur it in an oven at 120°C for 1 hour, and sinter it at 300°C for 1 hour to prepare a silicon dioxide anti-reflective coating.

[0129] S3: Preparation of antibacterial coating: 5g of octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride was added to 95g of ethanol to prepare a 5% (w / w) antibacterial modification solution. The above-mentioned silica antireflective coating was placed in this antibacterial modification solution and reacted for 24h. After rinsing three times with ethanol, it was placed in an oven at 115℃ for 1h to prepare the antibacterial coating.

[0130] S4: Preparation of anti-fouling coating: The above anti-reflective and antibacterial coating is placed in a 5% heptadecafluorodecyltriethoxysilane solution for 1 hour (solvent is ethanol), then rinsed 3 times with ethanol and placed in an oven at 120°C for 1 hour to prepare an antibacterial, anti-fouling and anti-reflective coating.

[0131] The anti-reflective, antibacterial, and anti-fouling coatings prepared in Examples 1 to 9 were tested. The transmittance, antibacterial rate, and oil residue of the anti-reflective, anti-fouling, and antibacterial coating obtained in Comparative Example 1 were tested. The test results are shown in Table 1.

[0132] Table 1 shows the test results of transmittance and antibacterial rate for Examples 1 to 9 and Comparative Example 1.

[0133] As shown in Table 1, the average light transmittance of Examples 1 to 6 (with a silica anti-reflective coating as the bottom layer) is greater than 93.4%, the antibacterial rate against Escherichia coli and Staphylococcus aureus is over 99.9%, and there is no residue of marker ink on the surface.

[0134] Comparative Example 1 involves first preparing an anti-fouling coating on an anti-reflective coating, and then preparing an antibacterial coating on the anti-fouling coating. The average light transmittance of the anti-reflective, anti-fouling, and antibacterial coating obtained in Comparative Example 1 is greater than 93.1%, but the antibacterial rate against Escherichia coli and Staphylococcus aureus is only 75%, and marker ink stains cannot be removed from the surface. Therefore, this anti-reflective, anti-fouling, and antibacterial coating does not have a stain-resistant effect.

[0135] Examples 7 to 9 describe the preparation of antibacterial coatings on antireflective coatings of acid-base mixed sol vegetation, and then the preparation of antifouling coatings on the antibacterial coatings. The average light transmittance of the antireflective, antibacterial and antifouling coatings obtained in Examples 7 to 9 is greater than 96.2%, the antibacterial rate against Escherichia coli and Staphylococcus aureus reaches more than 99.9%, and there is no residue of marker ink on the surface.

[0136] Therefore, the anti-reflective, antibacterial, and antifouling coating prepared in this invention must first have an antibacterial functional layer prepared before an antifouling functional layer is prepared.

[0137] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing an anti-reflective, antibacterial, and anti-fouling coating, characterized in that, Includes the following steps: S1: Add silane to the first solvent, and under the catalysis of an acid catalyst or an alkaline catalyst, stir and hydrolyze at 15℃~30℃ for 0.5h~24h, then age for more than 24h to obtain an acid-catalyzed inorganic nanosol or an alkaline-catalyzed inorganic nanosol; after uniformly mixing the prepared acid-catalyzed inorganic nanosol and alkaline-catalyzed inorganic nanosol in a set ratio, the final inorganic nanosol is obtained. S2: The inorganic nanosol is coated onto the surface of the substrate, dried, and then calcined at a first set temperature to prepare an anti-reflective coating on the surface of the substrate. S3: The anti-reflective coating is placed in an ammonium salt solution of a first set concentration for a first set time, then rinsed and dried to prepare an antibacterial coating on the surface of the anti-reflective coating; S4: The antibacterial coating is placed in a fluorosilane solution of a second set concentration for a second set time, then rinsed and dried to form an anti-fouling coating on the surface of the antibacterial coating.

2. The method for preparing the anti-reflective, antibacterial, and anti-fouling coating according to claim 1, characterized in that, The silane is tetraethyl orthosilicate, and the first solvent is ethanol or isopropanol.

3. The method for preparing the anti-reflective, antibacterial, and anti-fouling coating according to claim 2, characterized in that, The acid catalyst is any one of hydrochloric acid, acetic acid, or phosphoric acid, and the base catalyst is any one of sodium hydroxide, potassium hydroxide, or ammonia water with a mass fraction of 25% to 44%.

4. The method for preparing the anti-reflective, antibacterial, and anti-fouling coating according to claim 3, characterized in that, The mass ratio of each substance in the acid-catalyzed inorganic nanosol is silane: first solvent: acid catalyst = (0-10):(0-10):(0.1-5), and the mass ratio of each substance in the alkali-catalyzed inorganic nanosol is silane: first solvent: alkali catalyst = (0-10):(0-10):(0.1-5). The final inorganic nanosol has a mass ratio of 1:(0-10) for acid-catalyzed inorganic nanosol and 1:(0-10).

5. The method for preparing the anti-reflective, antibacterial, and anti-fouling coating according to claim 1, characterized in that, The coating method for applying the inorganic nanosol to the substrate surface is any one of the following: dip coating, roller coating, spray coating, or spin coating.

6. The method for preparing the anti-reflective, antibacterial, and anti-fouling coating according to claim 1, characterized in that, The first set concentration is 0.5% to 10% by mass, the solute in the ammonium salt solution is any one of octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, N,N-dimethyl-N-octadecylaminopropyltrimethoxysilane ammonium salt or dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, and the solvent in the ammonium salt solution is any one of ethanol, isopropanol or n-butanol.

7. The method for preparing the anti-reflective, antibacterial, and anti-fouling coating according to claim 1, characterized in that, In step S3, ethanol is used for rinsing.

8. The method for preparing the anti-reflective, antibacterial, and anti-fouling coating according to claim 1, characterized in that, The second set concentration is 0.2% to 5% by mass, the solute in the fluorosilane solution is either heptadecafluorodecyltriethoxysilane or tridecafluorooctyltriethoxysilane, and the solvent in the fluorosilane solution is either methyl nonafluorobutyl ether or ethanol.

9. The method for preparing the anti-reflective, antibacterial, and anti-fouling coating according to claim 1, characterized in that, In step S4, ethanol is used for rinsing.

10. An anti-reflective, antibacterial, and anti-fouling coating, prepared using the preparation method according to any one of claims 1 to 9, characterized in that, An anti-reflective, antibacterial, and anti-fouling coating is formed on the surface of a substrate. The anti-reflective, antibacterial, and anti-fouling coating includes an anti-reflective coating, an antibacterial coating, and an anti-fouling coating formed sequentially.

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