Anti-reflection, antibacterial and anti-fouling coating and preparation method thereof

Abstract

The invention relates to the technical field of coating compositions, in particular to an anti-reflection, antibacterial and anti-fouling coating and a preparation method thereof.The preparation method comprises the following steps that the surface of a substrate is coated with inorganic nano sol, the inorganic nano sol is calcined at the first set temperature after being dried, and the anti-reflection coating is prepared on the surface of the substrate; placing the anti-reflection coating in an ammonium salt solution with a first set concentration for a first set time, washing the anti-reflection coating with a second solvent, and drying the anti-reflection coating to prepare an antibacterial coating on the surface of the anti-reflection coating; and placing the antibacterial coating in a fluorosilane solution with a second set concentration for a second set time, washing the antibacterial coating with a third solvent, and drying the antibacterial coating to form an anti-fouling coating on the surface of the antibacterial coating. According to the anti-reflection, antibacterial and anti-pollution coating and the preparation method thereof, the problem that the anti-reflection coating is easily polluted by bacteria and oil stains is solved, and the anti-reflection, antibacterial and anti-pollution coating has the anti-reflection, antibacterial and anti-pollution functions.

Description

Technical Field

[0001] The 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 thereof. Background Art

[0002] With the rapid development of science and technology, visual screens are increasingly used in portable electronic devices, self-service office supplies, medical equipment, etc. However, the frequent use of interactive screens by users makes them a medium for the spread of pathogenic microorganisms between people. At the same time, these microorganisms can also spread from the hands to the environment, causing many infectious diseases. It is very difficult to disinfect touch screens using chemical disinfectants. Alcohol and other ingredients in disinfectants risk damaging the coating. Antibacterial technology can effectively reduce the growth and spread of microorganisms on the surface of these touch screens, but related research is very limited. In addition, excessive reflected light on the surface of the touch screen will have a negative impact on the user experience, so the coating applied to the interactive screen needs to have a certain anti-reflection ability. SiO 2 It has the advantages of good biocompatibility and low refractive index, and is an ideal material for preparing antireflective coatings. Therefore, it is necessary to develop SiO with antibacterial properties. 2 Coating is of great significance to its application on touch screen.

[0003] A recent promising strategy is to integrate antibacterial metal nanoparticles (NPs), such as Ag-NPs, Cu-NPs, and Zn-NPs, into coatings. Metal NPs kill bacteria mainly by releasing metal ions to disrupt bacterial metabolism. However, during long-term use, metal NPs continue to hydrolyze and migrate to the surface of the coating, resulting in a gradual decrease in the antibacterial properties of the coating.

[0004] Covalently grafting small molecules with bactericidal functions to the coating surface through surface chemical engineering is a promising alternative method. Ammonium salt (QAS) functionalized polymers are widely used to construct contact sterilization for textiles due to their effective antibacterial properties. However, the functionalized surface of QAS is prone to hygroscopicity, which will attract water containing bacteria to adhere to its surface, thereby forming a biofilm and reducing the antibacterial efficiency. Hydrophobic surfaces with low surface energy can effectively inhibit bacterial adhesion, but cannot inhibit bacterial reproduction. In addition, frequent finger touches will leave grease on the screen, which will increase the risk of bacterial transmission. Therefore, it is very urgent to study anti-bacterial and anti-fouling (dual anti-) functional anti-reflective coatings. Summary of the invention

[0005] The present invention aims to solve at least 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 a preparation method thereof, which solves the problem that the anti-reflective coating is easily contaminated by bacteria and oil stains, and makes it have the functions of anti-reflection, antibacterial and anti-fouling.

[0006] The present invention provides a method for preparing an anti-reflective, antibacterial and anti-fouling coating, comprising the following steps: Adding silane to the first solvent, stirring and hydrolyzing for 0.5 h to 24 h at 15° C. to 30° C. under the catalytic action of an acid catalyst or a base catalyst, and then aging for more than 24 h to obtain an acid-catalyzed inorganic nanosol or a base-catalyzed inorganic nanosol; uniformly mixing the prepared acid-catalyzed inorganic nanosol and the base-catalyzed inorganic nanosol in a set ratio to obtain a final inorganic nanosol; S2: coating the inorganic nano sol on the surface of the substrate, drying at 15° C. to 30° C., and then calcining at a first set temperature to prepare an anti-reflective coating on the surface of the substrate; S3: placing the anti-reflective coating in an ammonium salt solution of a first set concentration for a first set time, and then rinsing and drying, to prepare an antibacterial coating on the surface of the anti-reflective coating; S4: placing the antibacterial coating in a fluorosilane solution of a second set concentration for a second set time, and then rinsing and drying to form an antifouling coating on the surface of the antibacterial coating.

[0007] A further improvement of the method for preparing the anti-reflective, antibacterial and antifouling coating of the present invention is that the silane is ethyl orthosilicate, and the first solvent is ethanol or isopropanol.

[0008] A further improvement of the preparation method of the anti-reflective, antibacterial and antifouling coating of the present invention is 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, and ammonia water with a mass fraction of 25% to 44%.

[0009] A further improvement of the preparation method of the anti-reflective, antibacterial and antifouling coating of the present invention is that the mass ratio of the substances in the acid-catalyzed inorganic nanosol is silane: the first solvent: the acid catalyst = (0~10): (0~10): (0.1~5), the mass ratio of the substances in the base-catalyzed inorganic nanosol is silane: the first solvent: the base catalyst = (0~10): (0~10): (0.1~5), and the mass ratio of the acid-catalyzed inorganic nanosol and the base-catalyzed inorganic nanosol in the final inorganic nanosol is 1: (0~10).

[0010] A further improvement of the preparation method of the anti-reflective, antibacterial and antifouling coating of the present invention is that the inorganic nano-sol is coated on the surface of the substrate by any one of the following methods: pulling, rolling, spraying and spin coating.

[0011] A further improvement of the preparation method of the anti-reflective, antibacterial and antifouling 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 octadecyl dimethyl (3-trimethoxysilyl propyl) ammonium chloride, N,N-dimethyl-N-octadecyl aminopropyl trimethoxysilane ammonium salt or dimethyl octadecyl [3-(trimethoxysilyl) propyl] ammonium chloride, and the solvent in the ammonium salt solution is any one of ethanol, isopropanol or n-butanol.

[0012] A further improvement of the method for preparing the anti-reflective, antibacterial and antifouling coating of the present invention is that ethanol is used for washing in step S3.

[0013] A further improvement of the preparation method of the anti-reflective, antibacterial and antifouling coating of the present invention lies in 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.

[0014] A further improvement of the method for preparing the anti-reflective, antibacterial and antifouling coating of the present invention is that ethanol is used for washing in step S4.

[0015] An anti-reflective, anti-bacterial and anti-fouling coating is prepared using the preparation method as described above. The anti-reflective, anti-bacterial and anti-fouling coating is formed on the surface of a substrate. The anti-reflective, anti-bacterial and anti-fouling coating includes an anti-reflective coating, an anti-bacterial coating and an anti-fouling coating formed in sequence.

[0016] The above one or more technical solutions in the embodiments of the present invention have at least one of the following technical effects: (1) The coating prepared by the present invention has excellent anti-reflection performance and an average light transmittance of greater than 93.4%. The entangled molecular chains between the inorganic nanomaterials give it a dense continuous structure and ultra-low surface roughness, providing a platform for subsequent interface modification.

[0017] (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, with an antibacterial efficiency of over 80% against various bacteria such as Escherichia coli and Staphylococcus aureus.

[0018] (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.

[0019] (4) The coating prepared by the present invention has excellent anti-pollution performance. The grease on the coating surface cannot spread, and water droplets can slide off at a low tilt angle.

[0020] (5) The coating prepared by the present invention has super strong mechanical durability and can maintain long-lasting antibacterial, antifouling and anti-transmittance effects.

[0021] Additional aspects and advantages of the present invention will be given in part in the following description and in part will be obvious from the following description, or will be learned through practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0023] Figure 1 The present invention is a flow chart of a method for preparing an anti-reflective, antibacterial and anti-fouling coating.

[0024] Figure 2 This is a scanning electron microscope (SEM) photo of the anti-reflection coating obtained in Example 1.

[0025] Figure 3 This is a scanning electron microscope (SEM) photo of the anti-reflective antibacterial coating obtained in Example 1.

[0026] Figure 4 This is a scanning electron microscope (SEM) photo of the anti-reflective, antibacterial and antifouling coating obtained in Example 1.

[0027] Figure 5 This is the FTIR spectrum of the anti-reflective, antibacterial and antifouling coating obtained in Example 1.

[0028] Figure 6 This is the XPS spectrum of the anti-reflective, antibacterial and antifouling coating obtained in Example 1.

[0029] Figure 7 This is a high-magnification XPS spectrum of N in the anti-reflective, antibacterial and antifouling coating obtained in Example 1.

[0030] Figure 8 This is a scanning electron microscope (SEM) photo of the anti-reflection coating obtained in Comparative Example 1.

[0031] Fig. 9 This is a scanning electron microscope (SEM) photo of the anti-reflective and anti-fouling coating obtained in Comparative Example 1.

[0032] Fig.10 This is a scanning electron microscope (SEM) photo of the anti-reflective, anti-fouling and antibacterial coating obtained in Comparative Example 1. DETAILED DESCRIPTION

[0033] In order to make the purpose, technical scheme and advantages of the present invention clearer, the technical scheme of the present invention will be clearly and completely described below in conjunction with the drawings in the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention. The following embodiments are used to illustrate the present invention, but cannot be used to limit the scope of the present invention.

[0034] See also Figure 1 The present invention provides a method for preparing an anti-reflective, antibacterial and anti-fouling coating, comprising the following steps: S1: adding silane to the first solvent, stirring and hydrolyzing for 0.5h~24h at 15℃~30℃ under the catalytic action of an acid catalyst or a base catalyst, and then aging for more than 24h to obtain an acid-catalyzed inorganic nanosol or a base-catalyzed inorganic nanosol; uniformly mixing the prepared acid-catalyzed inorganic nanosol and the base-catalyzed inorganic nanosol in a set ratio to obtain a 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), and the mass ratio of each substance in the base-catalyzed inorganic nanosol is silane: first solvent: base catalyst = (0~10) : (0~10) : (0.1~5), and the mass ratio of the acid-catalyzed inorganic nanosol and the base-catalyzed inorganic nanosol in the final inorganic nanosol is 1: (0~10); S2: coating the inorganic nano sol on the surface of the substrate, drying at 15° C. to 30° C., and then calcining at a first set temperature to prepare an anti-reflective coating on the surface of the substrate; S3: placing the anti-reflective coating in an ammonium salt solution of a first set concentration for a first set time, and then washing with a second solvent and drying, to prepare an antibacterial coating on the surface of the anti-reflective coating; S4: placing the antibacterial coating in a fluorosilane solution of a second set concentration for a second set time, and then rinsing with a third solvent and drying to form an antifouling coating on the surface of the antibacterial coating.

[0035] Specifically, the silane is ethyl orthosilicate.

[0036] In another specific implementation case, an inorganic nano titanium dioxide anti-reflection coating can be formed on a substrate, and then an ammonium salt antibacterial coating is grafted on the titanium dioxide anti-reflection coating, and the inorganic nano titanium dioxide anti-reflection coating is formed by a sol method. The inorganic nano sol is prepared by using tetrabutyl titanate or titanium dioxide as a raw material.

[0037] It should be noted that the mass ratio of the acid-catalyzed inorganic nanosol to the base-catalyzed inorganic nanosol in the final inorganic nanosol can be 1:9, 1:5, 1:4, 1:2.5, 1:2, 1:1, etc.

[0038] Specifically, the first solvent is ethanol or isopropanol.

[0039] 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, and ammonia water with a mass fraction of 25% to 44%.

[0040] It should be noted that the optional mass fractions of ammonia water are 25%, 30%, 35%, 40%, 42% and 44%.

[0041] Preferably, the mass fraction of aqueous ammonia is 25%.

[0042] Specifically, the inorganic nano sol is coated on the surface of the substrate by any one of a Czochralski method, a roller coating method, a spray coating method, and a spin coating method.

[0043] It should be noted that the first set temperature can also be 100°C, 105°C, 110°C, 115°C, or 120°C.

[0044] Preferably, the first set temperature is 120°C.

[0045] Specifically, the first set concentration is a mass fraction of 0.5% to 10%, 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.

[0046] It should be noted that the first set concentration can be selected as 2%, 3%, 4%, or 5%.

[0047] Preferably, the first set concentration can be selected as 5%.

[0048] It should be noted that the first set time can be 20h, 24h, 28h, 30h, 35h, or 40h.

[0049] Preferably, the first set time is 24 hours, and the second solvent is ethanol; the operation method of washing with the second solvent and then drying is to wash with ethanol three times and dry in an oven at 115° C. for 1 hour.

[0050] Specifically, 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 (Novec7100) or ethanol.

[0051] It should be noted that the second set concentration that can be selected by those skilled in the art is 3% by mass, 4% by mass, 5% by mass, etc. The present invention does not impose any specific limitation on the value of the second set concentration.

[0052] It should be noted that the second set time can be 0.5h, 1h, 1.5h, 2h, 2.5h, or 3h.

[0053] Preferably, the second set time is 1 hour, and the third solvent is ethanol; the operation method of washing with the third solvent and then drying is to wash with ethanol three times and then place in an oven at 120° C. and dry for 1 hour.

[0054] The present invention also provides an anti-reflective, antibacterial and anti-fouling coating. The anti-reflective, antibacterial and anti-fouling coating is prepared using the above preparation method. The 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 in sequence.

[0055] The above one or more technical solutions in the embodiments of the present invention have at least one of the following technical effects: (1) The coating prepared by the present invention has excellent anti-reflection performance and an average light transmittance of greater than 93.4%. The entangled molecular chains between the inorganic nanomaterials give it a dense continuous structure and ultra-low surface roughness, providing a platform for subsequent interface modification.

[0056] (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, with an antibacterial efficiency of over 80% against various bacteria such as Escherichia coli and Staphylococcus aureus.

[0057] (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.

[0058] (4) The coating prepared by the present invention has excellent anti-pollution performance. The grease on the coating surface cannot spread, and water droplets can slide off at a low tilt angle.

[0059] (5) The coating prepared by the present invention has super strong mechanical durability and can maintain long-lasting antibacterial, antifouling and anti-transmittance effects.

[0060] The preparation method and characterization results of the anti-reflective, antibacterial and antifouling coating of the present invention are described below in conjunction with specific implementation cases.

[0061] Example 1 S1: 5 g of ethyl orthosilicate was added to 35.5 g of ethanol and stirred for 15 min. Then, 1.8 g of deionized water and 0.5 g of hydrochloric acid (12 mol / L) were added and the mixture was stirred for 1 h. Finally, the mixture was aged for 7 days to obtain an inorganic nano-sol of silicon dioxide.

[0062] S2: Immerse a completely clean glass plate in the inorganic nano-sol of silica, then pull it up at a uniform speed, dry it at room temperature for 10 minutes, pre-cure it at 120° C. in an oven for 1 hour, and sinter it at 300° C. for 1 hour to prepare an anti-reflective coating of silica.

[0063] S3: Add 2 g of octadecyldimethyl (3-trimethoxysilyl) ammonium chloride to 98 g of ethanol to prepare an antibacterial modified solution with a mass fraction of 2%; place the above antireflective coating in the antibacterial modified solution to react for 24 hours, rinse with ethanol three times, and place in an oven at 115°C for 1 hour to prepare an antibacterial coating.

[0064] S4: The anti-reflective antibacterial coating was placed in a 0.3% heptadecafluorodecyltriethoxysilane solution (the solvent was Novec 7100) for 1 hour, and then rinsed with ethanol three times and placed in a 120° C. oven for 1 hour to prepare an anti-reflective antibacterial antifouling coating.

[0065] The anti-reflective, antibacterial and antifouling coating obtained in Example 1 was subjected to characterization tests, wherein the testing equipment included: an ultraviolet spectrophotometer, a biochemical incubator, and a plate counter.

[0066] from Figure 2 It can be seen that the surface of the anti-reflection coating prepared in step S2 is very dense and flat.

[0067] from Figure 3 It can be seen that the surface of the anti-reflective coating prepared in step S3 after being connected with ammonium salt to form an anti-reflective antibacterial coating is very dense and flat.

[0068] from Figure 4 It can be seen that the surface of the anti-reflective, antibacterial and antifouling coating prepared in step S4 is very dense and flat.

[0069] from Figure 5 It can be seen that the anti-reflective antibacterial coating prepared in Example 1 has an optical conductivity of 2990 cm -1 The stretching vibration peak (CH) of ammonium salt appeared at the 40°C, while this peak was not detected on silica, indicating that the ammonium salt was successfully grafted onto the surface of the anti-reflective coating of silica.

[0070] from Figure 6The XPS spectrum of the anti-reflective, antibacterial and antifouling coating can be seen, and seven characteristic peaks of elements are detected, namely Si2p, Si2s, C1s, N1s, N+1s, O1s and F1s.

[0071] from Figure 7 It can be seen that the high-magnification XPS spectrum of N in the anti-reflective, antibacterial and antifouling coating shows that the antibacterial coating structure in the anti-reflective, antibacterial and antifouling coating is complete, and the preparation of the antifouling coating on the antibacterial coating will not affect the integrity of the antibacterial coating.

[0072] Comparative Example 1 S1: 5 g of ethyl orthosilicate was added to 35.5 g of ethanol and stirred for 15 min. Then, 1.8 g of deionized water and 0.5 g of hydrochloric acid (12 mol / L) were added and the mixture was stirred for 1 h. Finally, the mixture was aged for 7 days to obtain an inorganic nano-sol of silicon dioxide.

[0073] S2: Immerse a completely clean glass plate in the inorganic nano-sol of silica, then pull it up at a uniform speed, dry it at room temperature for 10 minutes, pre-cure it at 120° C. in an oven for 1 hour, and sinter it at 300° C. for 1 hour to prepare an anti-reflective coating of silica.

[0074] S3: The anti-reflective coating was placed in a 0.3% heptadecafluorodecyltriethoxysilane solution (the solvent was Novec 7100) for 1 hour, and then rinsed with ethanol three times and placed in a 120° C. oven for 1 hour to prepare an anti-reflective and anti-fouling coating.

[0075] S4: Add 2g of octadecyldimethyl (3-trimethoxysilyl) ammonium chloride to 98g of ethanol to prepare an antibacterial modified solution with a mass fraction of 2%; place the above anti-reflective coating in the antibacterial modified solution to react for 24 hours, rinse with ethanol three times, and place in an oven at 115°C for 1 hour to prepare an anti-reflective, anti-fouling, and antibacterial coating.

[0076] The difference between Comparative Example 1 and Example 1 is mainly that the preparation order of the antibacterial coating and the antifouling coating is adjusted. The anti-reflective antifouling antibacterial coating prepared in Comparative Example 1 was characterized and tested. Figure 8 , Fig. 9 and Fig.10 It can be seen that the surfaces of the anti-reflective coating, the anti-reflective anti-fouling coating and the anti-reflective anti-fouling antibacterial coating are very dense.

[0077] Example 2 S1: 5 g of ethyl orthosilicate was added to 35.5 g of ethanol and stirred for 15 min. Then, 1.8 g of deionized water and 0.5 g of hydrochloric acid (12 mol / L) were added and the mixture was stirred for 1 h. Finally, the mixture was aged for 7 days to obtain an inorganic nano-sol of silicon dioxide.

[0078] S2: Immerse a completely clean glass plate in the inorganic nano-sol of silica, then pull it up at a uniform speed, dry it at room temperature for 10 minutes, pre-cure it at 120° C. in an oven for 1 hour, and sinter it at 300° C. for 1 hour to prepare an anti-reflective coating of silica.

[0079] S3: Add 10g of ‌N,N-dimethyl-N-octadecylaminopropyltrimethoxysilane ammonium salt‌ to 90g of isopropanol to prepare an antibacterial modification solution with a mass fraction of 10%. Place the anti-reflective coating of silica in the antibacterial modification solution for 24h, rinse with ethanol three times, and place in a 120°C oven for 1h to prepare an antibacterial coating.

[0080] S4: The anti-reflective antibacterial coating was placed in a 0.8% heptadecafluorodecyltriethoxysilane solution (the solvent was Novec 7100) for 1 hour, and then rinsed with ethanol three times and placed in a 120° C. oven for 1 hour to prepare an anti-reflective antibacterial antifouling coating.

[0081] Example 3 S1: 5 g of ethyl orthosilicate was added to 35.5 g of ethanol and stirred for 15 min. Then, 1.8 g of deionized water and 0.5 g of hydrochloric acid (12 mol / L) were added and the mixture was stirred for 1 h. Finally, the mixture was aged for 7 days to obtain an inorganic nano-sol of silicon dioxide.

[0082] S2: Immerse a completely clean glass plate in the inorganic nano-sol of silica, then pull it up at a uniform speed, dry it at room temperature for 10 minutes, pre-cure it at 120° C. in an oven for 1 hour, and sinter it at 300° C. for 1 hour to prepare an anti-reflective coating of silica.

[0083] S3: Add 2.5 g of ‌N,N-dimethyl-N-octadecylaminopropyltrimethoxysilane ammonium salt‌ to 97.5 g of isopropanol to prepare an antibacterial modified solution with a mass fraction of 2.5%. The anti-reflective coating of silica is placed in the antibacterial modified solution for 24 hours, rinsed with ethanol three times, and placed in an oven at 115°C for 1 hour to prepare an antibacterial coating.

[0084] S4: The anti-reflective antibacterial coating was placed in a 1% tridecafluorooctyltriethoxysilane solution (the solvent was Novec 7100) for 1 hour, and then rinsed with ethanol three times and placed in a 120° C. oven for 1 hour to prepare an anti-reflective antibacterial antifouling coating.

[0085] Example 4 S1: 3 g of ethyl orthosilicate was added to 40.5 g of ethanol and stirred for 15 min. After adding 1 g of deionized water and 0.5 g of hydrochloric acid (12 mol / L), stirring was continued for 1 h. Finally, an inorganic nano-sol of silica was obtained in 7 days.

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

[0087] S3: 4 g of octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride was added to 96 g of ethanol to prepare an antibacterial modification solution with a mass fraction of 4%. The anti-reflective coating of the above silicon dioxide was placed in the antibacterial modification solution for 24 hours, rinsed with ethanol three times, and placed in an oven at 115°C for 1 hour to prepare an antibacterial coating.

[0088] S4: The anti-reflective antibacterial coating was placed in a 0.5% heptadecafluorodecyltriethoxysilane solution (the solvent was ethanol) for 1 hour, and then rinsed with ethanol three times and placed in a 120° C. oven for 1 hour to prepare an anti-reflective antibacterial antifouling coating.

[0089] Example 5 S1: 3 g of ethyl orthosilicate was added to 40.5 g of ethanol and stirred for 15 min. After adding 1 g of deionized water and 0.5 g of hydrochloric acid (12 mol / L), stirring was continued for 1 h. Finally, an inorganic nano-sol of silica was obtained in 7 days.

[0090] S2: Immerse a completely clean glass plate in the inorganic nano-sol of silica, then pull it up at a uniform speed, dry it at room temperature for 10 minutes, pre-cure it at 120° C. in an oven for 1 hour, and sinter it at 300° C. for 1 hour to prepare an anti-reflective coating of silica.

[0091] S3: Add 2g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride to 98g of n-butanol to prepare an antibacterial modification solution with a mass fraction of 2%. Place the anti-reflective coating of silica in the antibacterial modification solution for 24h, rinse with ethanol three times, and place in an oven at 115°C for 1h to prepare an antibacterial coating.

[0092] S4: The anti-reflective antibacterial coating was placed in a 0.8% heptadecafluorodecyltriethoxysilane solution (the solvent was ethanol) for 1 hour, and then rinsed with ethanol three times and placed in a 120° C. oven for 1 hour to prepare an anti-reflective antibacterial antifouling coating.

[0093] Example 6 S1: 3 g of ethyl orthosilicate was added to 40.5 g of isopropanol and stirred for 15 min. 1.5 g of deionized water and 0.5 g of acetic acid were added and stirred for 1 h. Finally, an inorganic nano-sol containing silicon dioxide was obtained after aging for 7 days.

[0094] S2: Immerse a completely clean glass plate in the inorganic nano-sol of silica, then pull it up at a uniform speed, dry it at room temperature for 10 minutes, pre-cure it at 120° C. in an oven for 1 hour, and sinter it at 300° C. for 1 hour to prepare an anti-reflective coating of silica.

[0095] S3: Add 2g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride to 98g of n-butanol to prepare an antibacterial modification solution with a mass fraction of 2%. Place the anti-reflective coating of silica in the antibacterial modification solution for 24h, rinse with ethanol three times, and place in an oven at 115°C for 1h to prepare an antibacterial coating.

[0096] S4: The anti-reflective antibacterial coating was placed in a 0.5% heptadecafluorodecyltriethoxysilane solution (the solvent was ethanol) for 1 hour, and then rinsed with ethanol three times and placed in a 120° C. oven for 1 hour to prepare an anti-reflective antibacterial antifouling coating.

[0097] Compared with Example 1, although the conditions of the acid catalyst and the solvent have changed, the test results of whether the ammonium salt is grafted on the silica in the anti-reflective antibacterial and antifouling coatings prepared by testing in Examples 2 to 6 are the same as those in Example 1, and will not be repeated here; compared with Example 1, although the conditions of the acid catalyst and the solvent have changed, the anti-reflective antibacterial and antifouling coatings prepared by testing have very dense and flat surfaces (characterization images are almost the same as those in Example 1), the anti-reflective antibacterial and antifouling coatings are very dense and flat (characterization images are almost the same as those in Example 1), the anti-reflective antibacterial and antifouling coatings are very dense and flat (characterization images are almost the same as those in Example 1); compared with Example 1, although the conditions of the acid catalyst and the solvent have changed, the FTIR spectrum of the anti-reflective antibacterial and antifouling coatings prepared by testing is almost the same as that in Example 1; the XPS spectra of the anti-reflective antibacterial and antifouling coatings of Examples 2 to 6 and the high-magnification XPS spectra of N are the same as those in Example 1, and the images of the characterization results are not repeated in this application.

[0098] Example 7 S1: Add 7g of ethyl orthosilicate to 50g of ethanol and stir for 15min, add 0.14g of ammonia water and continue stirring for 1h, and finally age for 7 days to obtain a base-catalyzed inorganic nanosol. Add 3g of ethyl 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, and finally age for 7 days to obtain an acid-catalyzed inorganic nanosol. The acid-catalyzed inorganic nanosol and the base-catalyzed inorganic nanosol were mixed in a mass ratio of 2:8 to prepare the final inorganic nanosol.

[0099] S2: Preparation of anti-reflection coating: A completely clean glass plate is immersed in the sol, then pulled up at a uniform speed, dried at room temperature for 10 minutes, pre-cured at 120°C in an oven for 1 hour, and sintered at 300°C for 1 hour to prepare an anti-reflection coating of silica.

[0100] S3: Preparation of antibacterial coating: 2g of octadecyldimethyl (3-trimethoxysilyl) ammonium chloride was added to 98g of ethanol to prepare an antibacterial modified solution with a mass fraction of 2%. The anti-reflective coating of silica was placed in the antibacterial modified solution for 24h, rinsed with ethanol three times, and placed in an oven at 115°C for 1h to prepare an antibacterial coating.

[0101] S4: Preparation of antifouling coating: The antireflective antibacterial coating was placed in a 1% heptadecafluorodecyltriethoxysilane solution (the solvent was ethanol) for 1 h, then rinsed with ethanol three times and placed in a 120° C. oven for 1 h to prepare an antireflective antibacterial antifouling coating.

[0102] Example 8 S1: Add 5g of ethyl orthosilicate to 55g of ethanol and stir for 15min, add 0.12g of ammonia water and continue stirring for 1h, and finally age for 7 days to obtain a base-catalyzed inorganic nanosol. Add 5g of ethyl 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, and finally age for 7 days to obtain an acid-catalyzed inorganic nanosol. The acid-catalyzed inorganic nanosol and the base-catalyzed inorganic nanosol were mixed in a mass ratio of 3:7 to prepare the final inorganic nanosol.

[0103] S2: Preparation of anti-reflection coating: A completely clean glass plate is immersed in the sol, then pulled up at a uniform speed, dried at room temperature for 10 minutes, pre-cured at 120°C in an oven for 1 hour, and sintered at 300°C for 1 hour to prepare an anti-reflection coating of silica.

[0104] S3: Preparation of antibacterial coating: 3 g of octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride was added to 97 g of ethanol to prepare an antibacterial modified solution with a mass fraction of 3%. The anti-reflective coating of silica was placed in the antibacterial modified solution for 24 h, rinsed with ethanol three times, and placed in an oven at 115°C for 1 h to prepare an antibacterial coating.

[0105] S4: Preparation of antifouling coating: The antireflective antibacterial coating was placed in a 0.5% heptadecafluorodecyltriethoxysilane solution (the solvent was ethanol) for 1 h, then rinsed with ethanol 3 times and placed in a 120° C. oven for 1 h to prepare an antireflective antibacterial antifouling coating.

[0106] Example 9 S1: Add 5g of tetraethyl orthosilicate to 50g of ethanol and stir for 15min, add 0.14g of ammonia water and continue stirring for 1h, and finally age for 7 days to obtain a base-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, and finally age for 7 days to obtain an acid-catalyzed inorganic nanosol. The acid-catalyzed inorganic nanosol and the base-catalyzed inorganic nanosol were mixed in a mass ratio of 1:9 to prepare the final inorganic nanosol.

[0107] S2: Preparation of anti-reflection coating: A completely clean glass plate is immersed in the sol, then pulled up at a uniform speed, dried at room temperature for 10 minutes, pre-cured at 120°C in an oven for 1 hour, and sintered at 300°C for 1 hour to prepare an anti-reflection coating of silica.

[0108] S3: Preparation of antibacterial coating: 5 g of octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride was added to 95 g of ethanol to prepare an antibacterial modified solution with a mass fraction of 5%. The anti-reflective coating of silica was placed in the antibacterial modified solution for 24 h, rinsed with ethanol three times, and placed in an oven at 115°C for 1 h to prepare an antibacterial coating.

[0109] S4: Preparation of antifouling coating: The antireflective antibacterial coating was placed in a 5% heptadecafluorodecyltriethoxysilane solution (the solvent was ethanol) for 1 h, then rinsed with ethanol three times and placed in a 120° C. oven for 1 h to prepare an antibacterial, antifouling, antireflective coating.

[0110] The anti-reflective, anti-bacterial and anti-fouling coatings prepared in the above Examples 1 to 9 were tested, and the anti-reflective, anti-fouling and anti-bacterial coating prepared in Comparative Example 1 was tested for light transmittance, antibacterial rate and oil residue. The test results are shown in Table 1.

[0111] Table 1 Test results of light transmittance and antibacterial rate of Examples 1 to 9 and Comparative Example 1

[0112] As shown in Table 1, the average light transmittance of Examples 1 to 6 (the bottom layer is an anti-reflective coating of silicon dioxide) is greater than 93.4%, the antibacterial rate against Escherichia coli and Staphylococcus aureus is more than 99.9%, and no marker pen oil stains remain on the surface.

[0113] Comparative Example 1 is to first prepare an anti-fouling coating on the anti-reflective coating, and then prepare an antibacterial coating on the anti-fouling coating. The average light transmittance of the anti-reflective, anti-fouling, antibacterial coating obtained in Comparative Example 1 is greater than 93.1%, and the antibacterial rate against Escherichia coli and Staphylococcus aureus is only 75%, and the oil stains of the marker pen cannot be removed on the surface. The anti-reflective, anti-fouling, antibacterial coating does not have an anti-fouling effect.

[0114] Examples 7 to 9 are for preparing an antibacterial coating on the anti-reflective coating of acid-alkali mixed sol vegetation, and then preparing an anti-fouling coating on the antibacterial coating. The average light transmittance of the anti-reflective, antibacterial and anti-fouling coatings obtained in Examples 7 to 9 is greater than 96.2%, and the antibacterial rate against Escherichia coli and Staphylococcus aureus is more than 99.9%, and there is no residue of marker pen stains on the surface.

[0115] Therefore, the anti-reflective, anti-bacterial and anti-fouling coating prepared by the present invention must first prepare the anti-bacterial functional layer and then prepare the anti-fouling functional layer.

[0116] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions 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: The steps include: S1: adding silane to the first solvent, stirring and hydrolyzing the mixture at 15°C to 30°C for 0.5h to 24h under the catalytic action of an acid catalyst or a base catalyst, and then aging the mixture for more than 24h to obtain an acid-catalyzed inorganic nanosol or a base-catalyzed inorganic nanosol; uniformly mixing the prepared acid-catalyzed inorganic nanosol and the base-catalyzed inorganic nanosol in a set ratio to obtain a final inorganic nanosol; S2: coating the inorganic nano sol on the surface of the substrate, drying it and calcining it at a first set temperature to prepare an anti-reflective coating on the surface of the substrate; S3: placing the anti-reflective coating in an ammonium salt solution of a first set concentration for a first set time, and then rinsing and drying, to prepare an antibacterial coating on the surface of the anti-reflective coating; S4: placing the antibacterial coating in a fluorosilane solution of a second set concentration for a second set time, and then rinsing and drying to form an antifouling 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, anti-bacterial 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, and ammonia water with a mass fraction of 25% to 44%.

4. The method for preparing the anti-reflective, anti-bacterial 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), the mass ratio of each substance in the base-catalyzed inorganic nanosol is silane: first solvent: base catalyst = (0-10): (0-10): (0.1-5), and the mass ratio of the acid-catalyzed inorganic nanosol to the base-catalyzed inorganic nanosol in the final inorganic nanosol is 1: (0-10).

5. The method for preparing the anti-reflective, antibacterial and anti-fouling coating according to claim 1, characterized in that: The inorganic nano sol is coated on the surface of the substrate by any one of a Czochralski method, a rolling method, a spraying method and a spin coating method.

6. The method for preparing the anti-reflective, anti-bacterial and anti-fouling coating according to claim 1, characterized in that: The first set concentration is a mass fraction of 0.5% to 10%, the solute in the ammonium salt solution is any one of octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, N,N-dimethyl-N-octadecylaminopropyl trimethoxysilane 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 washing.

8. The method for preparing the anti-reflective, antibacterial and antifouling coating according to claim 1, characterized in that: The second set concentration is a mass fraction of 0.2% to 5%, 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.

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

10. An anti-reflective, anti-bacterial and anti-fouling coating, prepared by the preparation method according to any one of claims 1 to 9, characterized in that: The anti-reflective, anti-bacterial and anti-fouling coating is formed on the surface of the substrate, and the anti-reflective, anti-bacterial and anti-fouling coating comprises an anti-reflective coating, an anti-bacterial coating and an anti-fouling coating which are formed in sequence.

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