An antifogging resin coating material, a method for preparing the same, and an application thereof

Abstract

The application discloses an amphiphilic anti-fog resin coating and a preparation method and application thereof, relates to the technical field of anti-fog coatings, and aims at solving the problem that there is no mechanical stable, long-lasting anti-fog effect and significant bacteriostatic effect in the prior art.The technical points of the application include: S1. Preparation of amphiphilic functional siloxane: mixing mercaptosiloxane monomer, hydrophobic monomer, hydrophilic monomer, photoinitiator and solvent I, then using ultraviolet light to initiate thiol-olefin click reaction, and then removing solvent I to prepare amphiphilic functional siloxane; S2. Preparation of fluorine-containing silicon resin coating with amphiphilic segment: mixing and stirring the amphiphilic functional siloxane, tetraethyl orthosilicate, alkylsiloxane monomer, fluorine-containing siloxane monomer and solvent II, and then reacting in a sol-gel system with an acidic catalyst to obtain a fluorine-containing silicon resin with an amphiphilic segment; and performing ultrasonic oscillation on the fluorine-containing silicon resin with the amphiphilic segment to obtain a functional resin coating.

Description

Technical Field

[0001] This invention relates to the field of anti-fog coating technology, and more specifically, to an amphiphilic anti-fog resin coating, its preparation method, and its application. Background Technology

[0002] Fogging caused by water condensation on modern engineering equipment, medical devices, automotive / aircraft viewing windows, and transparent exterior glass of buildings can pose hazards such as safety risks, medical adverse effects, and traffic accidents. Therefore, there is a need to develop a highly transparent anti-fogging coating technology that is easy to operate and provides excellent anti-fogging performance for various transparent devices.

[0003] Traditionally developed antifog coatings are primarily (super)hydrophilic and (super)hydrophobic, achieving antifog protection through ultra-high water absorption and water droplet repulsion, respectively. However, the swelling effect of hydrophilic materials leads to their failure, and the complexity of superhydrophobic material preparation and structural stability issues also limit their application. Amphiphilic coatings combine the advantages of both technologies and can be applied to the field of antifog coating technology. However, existing technologies lack mechanically stable, durable antifog effects, and significant antibacterial properties, making them difficult to apply to water mist protection for medical equipment, viewing windows, and other devices. Summary of the Invention

[0004] The technical problem to be solved by this invention is:

[0005] There is a lack of amphiphilic antifog resin coatings in the current technology that have mechanical stability, long-lasting antifog effect, and significant antibacterial effect.

[0006] The technical solution adopted by the present invention to solve the above-mentioned technical problems is as follows:

[0007] This invention provides a method for preparing an amphiphilic antifogging resin coating, comprising the following steps:

[0008] S1. Preparation of amphiphilic functional siloxanes: A mercaptosiloxane monomer, a hydrophobic monomer, a hydrophilic monomer, a photoinitiator and solvent 1 are mixed, and then a thiol-olefin click reaction is initiated by ultraviolet light. After that, solvent 1 is removed to prepare amphiphilic functional siloxanes.

[0009] S2. Preparation of fluorinated silicone resin coating with amphiphilic segments: The amphiphilic functional siloxane, tetraethyl orthosilicate, alkyl siloxane monomer, fluorinated siloxane monomer and solvent are mixed and stirred, and reacted in a sol-gel system with an acidic catalyst to obtain fluorinated silicone resin with amphiphilic segments; the fluorinated silicone resin with amphiphilic segments is subjected to ultrasonic vibration to obtain functional resin coating.

[0010] Further, in step S1, the mercaptosiloxane monomer is selected from one or more of (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)triethoxysilane, or 11-mercaptoundecyltrimethoxysilane; the hydrophobic monomer is selected from one or more of butyl methacrylate, hexyl methacrylate, sec-butyl methacrylate, tetradecyl methacrylate, n-octyl methacrylate, lauryl methacrylate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, stearate methacrylate, dodecafluoroheptyl methacrylate, or octadecyl methacrylate; and the hydrophilic monomer is selected from one or more of N-vinylpyrrolidone, polyethylene glycol dimethacrylate, polyethylene glycol methyl ether acrylate, or polyethylene glycol methyl ether methacrylate.

[0011] Further, in step S1, the mass ratio of mercaptosiloxane monomer, hydrophobic monomer, and hydrophilic monomer is 1:(0.1-5):(0.1-10).

[0012] Further, in step S2, the alkylsiloxane monomer is selected from one or more of propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, n-octyltriethoxysilane, n-decyltriethoxysilane, or n-octadecyltriethoxysilane; the fluorinated siloxane monomer is selected from one or more of (3,3,3-trifluoropropyl)trimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 1H,1H,2H,2H-perfluorodecyltriethoxysilane, or 1H,1H,2H,2H-perfluorooctyltrimethoxysilane.

[0013] Further, in step S2, the mass ratio of tetraethyl orthosilicate, alkylsiloxane monomer, fluorinated siloxane monomer, and amphiphilic functional siloxane is 1:(0.2-1.5):(0.01-1.0):(0.01-1.0).

[0014] This invention provides an amphiphilic antifog resin coating, which is prepared by any of the methods described in the above technical solutions.

[0015] The present invention provides an amphiphilic antifog coating, which is prepared by applying the above-mentioned amphiphilic antifog resin coating to the surface of a substrate to form a wet film, and further drying the wet film.

[0016] Furthermore, the thickness of the wet coating film is 10-50 μm.

[0017] Furthermore, the substrate includes one or more of glass, polymethyl methacrylate sheet, polycarbonate sheet, or polyethylene terephthalate sheet.

[0018] This invention provides the application of the aforementioned amphiphilic antifog coating in the surface protection of medical endoscopes, medical devices, automotive / aircraft viewing windows, and transparent external equipment of buildings.

[0019] Compared with the prior art, the beneficial effects of the present invention are:

[0020] The anti-fog coating of the present invention is amphiphilic. The hydrophilic groups can effectively absorb water molecules in the environment to form a thin layer to achieve anti-fog, while the hydrophobic groups play an anchoring role, making it less susceptible to water damage. This improves the coating's resistance to swelling and mechanical stability, making the anti-fog effect more durable.

[0021] The preparation process of the amphiphilic antifog coating of this invention does not require heating equipment, thus saving energy consumption during the preparation process. The coating only requires a short high-temperature curing process to obtain a stable cured coating, which has the advantages of low energy consumption and high efficiency.

[0022] Through the synergistic effect of hydrophilic / hydrophobic groups, the coating of this invention possesses excellent optical transparency, anti-fogging, antibacterial and anti-icing properties, and has a wide range of applications. Attached Figure Description

[0023] Figure 1 This is a graph showing the test results of the coating under ultraviolet-visible light spectrum in an embodiment of the present invention;

[0024] Figure 2 Image 1 shows the coating in an embodiment of the present invention;

[0025] Figure 3 Image 2 shows the coating in an embodiment of the present invention. Detailed Implementation

[0026] To enable those skilled in the art to better understand the present invention, exemplary embodiments or examples of the present invention will be described below in conjunction with the accompanying drawings. Obviously, the described embodiments or examples are merely some, not all, of the embodiments or examples of the present invention. All other embodiments or examples obtained by those skilled in the art based on the embodiments or examples of the present invention without inventive effort should fall within the scope of protection of the present invention.

[0027] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0028] In a typical embodiment, the present invention provides a method for preparing an amphiphilic antifogging resin coating, comprising the following steps:

[0029] S1. Preparation of amphiphilic functional siloxanes: A mercaptosiloxane monomer, a hydrophobic monomer, a hydrophilic monomer, a photoinitiator and solvent 1 are mixed and stirred, and then a thiol-olefin click reaction is initiated by ultraviolet light. After that, solvent 1 is removed to prepare amphiphilic functional siloxanes.

[0030] S2. Preparation of fluorinated silicone resin coating with amphiphilic segments: The amphiphilic functional siloxane, tetraethyl orthosilicate, alkyl siloxane monomer, fluorinated siloxane monomer and solvent are mixed and stirred, and then reacted in a sol-gel system with dilute hydrochloric acid as a catalyst to obtain fluorinated silicone resin with amphiphilic segments; the fluorinated silicone resin with amphiphilic segments is subjected to ultrasonic vibration to obtain functional resin coating.

[0031] In this embodiment, step 1 uses a thiol-olefin click reaction to prepare amphiphilic functional siloxanes. Under the combined action of ultraviolet light and a photocatalyst, the thiol is excited to become a thio radical, which then attacks the carbon-carbon double bonds of the hydrophobic and hydrophilic monomers, followed by an addition reaction, ultimately generating a functional siloxane with both hydrophilic and hydrophobic groups. In step S2, in the sol-gel system, under the catalysis of dilute hydrochloric acid in the acidic medium of the sol-gel system, tetraethyl orthosilicate and other siloxanes undergo ester bond hydrolysis to generate abundant silanol groups. Then, the silanol groups undergo a condensation reaction to generate the main chain Si-O-Si, while the hydrophobic alkyl groups, fluorinated groups, and amphiphilic segments on the side chains are retained. During ultrasonic vibration, the reaction products are uniformly dispersed, ensuring that the polymer is uniformly dispersed on the substrate surface during coating.

[0032] In a typical embodiment, preferably, in step S1, the mercaptosiloxane monomer is selected from one or more of (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)triethoxy, or 11-mercaptoundecyltrimethoxysilane; the hydrophobic monomer is selected from one or more of butyl methacrylate, hexyl methacrylate, sec-butyl methacrylate, tetradecyl methacrylate, n-octyl methacrylate, lauryl methacrylate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, stearate methacrylate, dodecafluoroheptyl methacrylate, or octadecyl methacrylate; the hydrophilic monomer is selected from one or more of N-vinylpyrrolidone, polyethylene glycol dimethacrylate, polyethylene glycol methyl ether acrylate, or polyethylene glycol methyl ether methacrylate; and the solvent is selected from one or both of methanol and ethanol. In this embodiment, both the hydrophobic and hydrophilic monomer molecules contain reactive double bonds, ultimately achieving a thiol-olefin click reaction.

[0033] In a typical embodiment, preferably, in step S1, the mass ratio of the mercaptosiloxane monomer, the hydrophobic monomer, and the hydrophilic monomer is 1:(0.1-5):(0.1-10).

[0034] In a typical embodiment, preferably, in step S2, the alkylsiloxane monomer is selected from one or more of propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, n-octyltriethoxysilane, n-decyltriethoxysilane, or n-octadecyltriethoxysilane; the fluorinated siloxane monomer is selected from one or more of (3,3,3-trifluoropropyl)trimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 1H,1H,2H,2H-perfluorodecyltriethoxysilane, or 1H,1H,2H,2H-perfluorooctyltrimethoxysilane; and the solvent is selected from one or more of methanol, ethanol, and isopropanol.

[0035] In step S2 of this embodiment, the alkylsiloxane monomers used can all undergo hydrolysis in the sol-gel system to generate intermediates with silanol groups. Each intermediate will undergo a condensation reaction to generate a resin with a Si-O-Si main chain structure.

[0036] The solvent used in this invention is an environmentally friendly alcohol solvent, which has the advantages of low toxicity, non-carcinogenicity and biodegradability, and has little harm to the environment.

[0037] In a typical embodiment, preferably, in step S2, the mass ratio of tetraethyl orthosilicate, alkylsiloxane monomer, fluorinated siloxane monomer, and amphiphilic functional siloxane is 1:(0.2-1.5):(0.01-1.0):(0.01-1.0).

[0038] In a typical embodiment, the present invention provides an amphiphilic antifog resin coating, which is prepared by the above method.

[0039] In a typical embodiment, the present invention provides an amphiphilic antifog coating, which is prepared by applying the above-mentioned amphiphilic antifog resin coating to the surface of a substrate to form a wet film, and further drying the wet film.

[0040] In a typical embodiment, preferably, the coating is applied by one of brushing, spin coating, scraping, and dip coating. When brushing or scraping, the thickness of the wet film is 10-50 μm to ensure the stability and uniformity of the coating curing process. When spin coating, the rotation speed exceeds 2000 rpm.

[0041] In a typical embodiment, preferably, the substrate comprises one or more of glass, polymethyl methacrylate sheet, polycarbonate sheet, or polyethylene terephthalate sheet.

[0042] In a typical embodiment, the preferred drying conditions for the wet film coating are: standing at 60-100°C for 0.1-6 hours to gradually release the solvent and water; and then standing in a ventilated environment at 15-30°C for 4 to 14 days.

[0043] In one typical embodiment, the present invention provides the application of the amphiphilic antifog coating in the surface protection of medical endoscopes, medical devices, automotive / aircraft viewing windows, and transparent external devices of buildings.

[0044] Example 1

[0045] S1. 1.96 g of (3-mercaptopropyl)trimethoxysilane, 5.68 g of butyl methacrylate, 4.44 g of N-vinylpyrrolidone and 10 mL of anhydrous ethanol solvent were mixed and stirred, 0.36 g of benzoin dimethyl ether was added, and then a thiol-olefin click reaction was initiated using ultraviolet light. After that, the solvent was removed to prepare an amphiphilic functional siloxane.

[0046] S2. Mix and stir 0.96g of amphiphilic functional siloxane, 2.08g of tetraethyl orthosilicate, 2.76g of n-octyltriethoxysilane, 0.22g of (3,3,3-trifluoropropyl)trimethoxysilane and 4.0g of isopropanol, and then react in a sol-gel system at 25°C for 24 hours to obtain a fluorinated silicone resin with amphiphilic segments; sonicate the fluorinated silicone resin with amphiphilic segments for 15 minutes to obtain a functional resin solution;

[0047] S3. Apply the functional anti-fog resin to the surface of the glass slide using a spin coating method;

[0048] S4. Place the coating in a 60°C forced-air drying oven and let it stand for 2 hours, then place it in a fume hood and let it stand at 25°C for 7 days to obtain an anti-fog coating.

[0049] The coating-related properties and shape tests are as follows:

[0050] Bacterial adhesion inhibition performance test: Control glass slides and samples coated with the coating from Example 1 were placed in cultured Escherichia coli or Staphylococcus aureus nutrient solutions for 18 hours. Afterwards, the control glass slides and the coating from Example 1 were removed, and the bacteria on the sample surface were washed off using liquid culture medium. The diluted bacteria were then coated onto solid culture medium and incubated for 12 hours. The number of bacterial colonies adhering to the surface of the control glass slides and the coated samples from Example 1 was calculated. Using the number of bacterial colonies on the surface of the control glass slides as a benchmark, the bacterial adhesion inhibition rate of the coating surface in Example 1 was calculated. The results are as follows:

[0051] The coating surface showed an inhibition rate of 84.2% against Staphylococcus aureus and 92.4% against Escherichia coli.

[0052] Anti-fog performance test: The control glass slide and the coating from Example 1 were placed 3 cm above an 80°C water bath. When both the glass and coating surfaces were completely covered by water mist, they were simultaneously placed in a room temperature environment. The time it took for the water mist to completely dissipate was compared to verify the coating's performance in promoting water mist removal. The results are as follows:

[0053] The water mist dissipation time on the glass was 95s; the water mist dissipation time on the coating was 24.6s, and the water mist removal time on the coating was shortened by more than 2 times.

[0054] The transmittance of the coating in Example 1 in the 380-780nm wavelength range was detected using ultraviolet-visible spectroscopy. Figure 1 As shown, the light transmittance of the coating exceeds 95%, indicating that the coating of the present invention has high optical transmittance.

[0055] The coating of Example 1, prepared by spin coating on a glass slide (7.5 cm × 2.5 cm) as a substrate, is as follows: Figure 2 As shown, the text at the bottom is clearly visible through the coating and the glass substrate, proving the coating's high transparency.

[0056] The coating of Example 1, prepared by brushing on a glass (20 cm × 10 cm) substrate, is as follows: Figure 3 As shown, the high regularity of the coating indicates that a regular coating can be obtained by either spin coating or brush coating.

[0057] Example 2

[0058] The difference between this embodiment and Example 1 is that in S1, the hydrophobic monomer is butyl methacrylate with a mass of 2.84g, the hydrophilic monomer is N-vinylpyrrolidone with a mass of 6.66g, and the mass of benzoin dimethyl ether is 0.34g. The rest is the same as in Example 1.

[0059] The results of the bacterial adhesion inhibition performance test are as follows:

[0060] The coating inhibited Staphylococcus aureus by 87.2% and Escherichia coli by 94.2%.

[0061] The anti-fog performance test results are as follows:

[0062] Example 2: Water mist dissipation time on the coating: 32.5s.

[0063] The transmittance of the coating in the 380-780 nm wavelength range was measured using ultraviolet-visible spectroscopy. In Example 2, the transmittance of the coating exceeded 95%, demonstrating the high optical transmittance of the coating of this invention. The results are as follows: Figure 1 As shown.

[0064] While the present invention has been disclosed above, its scope of protection is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and all such changes and modifications will fall within the scope of protection of the present invention.

Claims

1. A method for preparing an amphiphilic antifogging resin coating, characterized in that, Includes the following steps: S1. Preparation of amphiphilic functional siloxanes: A mercaptosiloxane monomer, a hydrophobic monomer, a hydrophilic monomer, a photoinitiator and solvent 1 are mixed, and then a thiol-olefin click reaction is initiated by ultraviolet light. After that, solvent 1 is removed to prepare amphiphilic functional siloxanes. S2. Preparation of fluorinated silicone resin coating with amphiphilic segments: The amphiphilic functional siloxane, tetraethyl orthosilicate, alkyl siloxane monomer, fluorinated siloxane monomer and solvent are mixed and stirred, and reacted in a sol-gel system with an acidic catalyst to obtain fluorinated silicone resin with amphiphilic segments; the fluorinated silicone resin with amphiphilic segments is subjected to ultrasonic vibration to obtain functional resin coating.

2. The method for preparing the amphiphilic antifog resin coating according to claim 1, characterized in that, In step S1, the mercaptosiloxane monomer is selected from one or more of (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)triethoxysilane, or 11-mercaptoundecyltrimethoxysilane; the hydrophobic monomer is selected from one or more of butyl methacrylate, hexyl methacrylate, sec-butyl methacrylate, tetradecyl methacrylate, n-octyl methacrylate, lauryl methacrylate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, stearate methacrylate, dodecafluoroheptyl methacrylate, or octadecyl methacrylate; and the hydrophilic monomer is selected from one or more of N-vinylpyrrolidone, polyethylene glycol dimethacrylate, polyethylene glycol methyl ether acrylate, or polyethylene glycol methyl ether methacrylate.

3. The method for preparing the amphiphilic antifogging resin coating according to claim 2, characterized in that, In step S1, the mass ratio of mercaptosiloxane monomer, hydrophobic monomer, and hydrophilic monomer is 1:(0.1-5):(0.1-10).

4. The method for preparing the amphiphilic antifog resin coating according to claim 3, characterized in that, In step S2, the alkylsiloxane monomer is selected from one or more of propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, n-octyltriethoxysilane, n-decyltriethoxysilane, or n-octadecyltriethoxysilane; the fluorinated siloxane monomer is selected from one or more of (3,3,3-trifluoropropyl)trimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 1H,1H,2H,2H-perfluorodecyltriethoxysilane, or 1H,1H,2H,2H-perfluorooctyltrimethoxysilane.

5. The method for preparing the amphiphilic antifogging resin coating according to claim 4, characterized in that, In step S2, the mass ratio of tetraethyl orthosilicate, alkylsiloxane monomer, fluorinated siloxane monomer, and amphiphilic functional siloxane is 1:(0.2-1.5):(0.01-1.0):(0.01-1.0).

6. An amphiphilic antifogging resin coating, characterized in that, The resin coating is prepared by the method described in any one of claims 1-5.

7. An amphiphilic anti-fog coating, characterized in that, The coating is prepared by applying the amphiphilic antifog resin coating of claim 6 to the surface of a substrate to form a wet film, and then further drying the wet film.

8. The amphiphilic anti-fog coating according to claim 7, characterized in that, The thickness of the wet coating film is 10-50 μm.

9. The amphiphilic anti-fog coating according to claim 8, characterized in that, The substrate includes one or more of glass, polymethyl methacrylate sheet, polycarbonate sheet, or polyethylene terephthalate sheet.

10. The application of the amphiphilic antifog coating of claim 7 in the surface protection of medical endoscopes, medical devices, automotive / aircraft viewing windows, and transparent external equipment of buildings.

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