A quaternary ammonium salt polymer, a double-crosslinking wear-resistant transparent anti-fog water-based paint and a coating thereof

Abstract

The application provides a kind of quaternary ammonium salt polymer, double crosslinking wear-resistant transparent anti-fog water-based paint and coating thereof, and relates to the technical field of coating material.The application provides a kind of quaternary ammonium salt polymer, which is prepared by the method comprising the following steps: mixing dimethylaminoethyl methacrylate, acrylic acid, initiator and organic solvent to carry out free radical polymerization reaction to obtain a primary polymer; the primary polymer, 1-bromoheptane and organic solvent are mixed to carry out quaternary ammonium reaction to obtain the quaternary ammonium salt polymer.The application provides a kind of double crosslinking wear-resistant transparent anti-fog water-based paint, and the components include the quaternary ammonium polymer, water, trifunctional aziridine crosslinking agent, polyethylene glycol diacrylate and photoinitiator.The water-based paint provided by the application can form a double crosslinking structure after ultraviolet curing, has the advantages of long-lasting anti-fog effect (can realize more than 20 days of long-lasting anti-fog), good wear resistance and high light transmission.

Description

Technical Field

[0001] This invention relates to the field of coating materials technology, and in particular to a quaternary ammonium salt polymer, a double crosslinked wear-resistant transparent anti-fog waterborne coating and its coating. Background Technology

[0002] Transparent substrates possess excellent optical properties and are widely used in daily life. However, during actual use, temperature changes due to environmental variations can cause moisture in the air to condense on the surface of the transparent substrate, forming fog. Fog formation not only significantly reduces the transparency of the substrate, causing inconvenience, but also poses several potential hazards. Therefore, the development of anti-fog coatings has received widespread attention from researchers.

[0003] Most anti-fog coatings currently on the market contain volatile organic compounds, which not only pollute the environment but also harm human health, posing serious risks. Furthermore, most anti-fog coatings suffer from poor abrasion resistance, which significantly limits their application. Therefore, the development of abrasion-resistant and environmentally friendly water-based anti-fog coatings is urgently needed. Summary of the Invention

[0004] In view of this, the purpose of this invention is to provide a quaternary ammonium salt polymer, a double-crosslinked wear-resistant transparent anti-fog waterborne coating, and the coating thereof. The waterborne coating formed by the quaternary ammonium salt polymer, a aziridine crosslinking agent, and polyethylene glycol diacrylate provided by this invention, after UV curing, yields a transparent wear-resistant coating with durable anti-fog properties.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a quaternary ammonium salt polymer, prepared by a method comprising the following steps:

[0007] Dimethylaminoethyl methacrylate, acrylic acid, initiator and organic solvent were mixed and subjected to free radical polymerization to obtain the primary polymer;

[0008] The primary polymer, 1-bromoheptane, and an organic solvent are mixed and subjected to a quaternization reaction to obtain the quaternary ammonium salt polymer.

[0009] Preferably, the mass ratio of dimethylaminoethyl methacrylate to acrylic acid is 8:1 to 11:1.

[0010] Preferably, the free radical polymerization reaction is carried out at a temperature of 75–85°C for 10–13 hours.

[0011] Preferably, the mass ratio of the primary polymer to 1-bromoheptane is 1:1.4 to 1:1.7.

[0012] Preferably, the quaternization reaction is carried out at a temperature of 75–85°C for 10–13 hours.

[0013] This invention provides a double crosslinked wear-resistant transparent anti-fog waterborne coating, the components of which include a quaternized polymer, water, a trifunctional aziridine crosslinking agent, polyethylene glycol diacrylate, and a photoinitiator; the quaternized polymer is the quaternary ammonium salt polymer described in the above technical solution.

[0014] Preferably, the photoinitiator includes one or more of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2-hydroxy-2-methylphenylacetone, and benzophenone.

[0015] Preferably, the mass of the trifunctional aziridine crosslinking agent is 15-22% of the mass of the quaternized polymer, the mass of the polyethylene glycol diacrylate is 1.8-2.2% of the mass of the quaternized polymer, the mass of the photoinitiator is 8-12% of the mass of the polyethylene glycol diacrylate, and the solid content of the double crosslinked wear-resistant transparent anti-fog waterborne coating is 10-20 wt%.

[0016] This invention provides a double crosslinked wear-resistant transparent anti-fog coating, which is obtained by coating the substrate surface with the double crosslinked wear-resistant transparent anti-fog water-based coating described in the above technical solution and then curing it with ultraviolet light.

[0017] Preferably, the UV power for UV curing is 800-1000W, and the curing time is 20-40min.

[0018] This invention provides a quaternary ammonium salt polymer, prepared by a method comprising the following steps: mixing dimethylaminoethyl methacrylate, acrylic acid, an initiator, and an organic solvent for free radical polymerization to obtain a primary polymer; and mixing the primary polymer, 1-bromoheptane, and an organic solvent for quaternization to obtain the quaternary ammonium salt polymer. The quaternary ammonium salt polymer provided by this invention exhibits hydrophilic properties and is readily soluble in water. When used in the preparation of hydrophilic coatings, the resulting coating, containing quaternary ammonium salts, can absorb water droplets condensing on its surface, thus providing an anti-fogging effect. Furthermore, its highly cross-linked structure makes the coating relatively stable, maintaining the anti-fogging effect for a longer period, and it also exhibits good wear resistance.

[0019] This invention provides a dual-crosslinked, wear-resistant, transparent, anti-fog waterborne coating, comprising a quaternized polymer, water, a trifunctional aziridine crosslinking agent, polyethylene glycol diacrylate, and a photoinitiator; the quaternized polymer is the quaternary ammonium salt polymer described in the previous technical solution. The waterborne coating provided by this invention, after UV curing, allows the aziridine crosslinking agent to react with the carboxyl groups contained in the quaternized polymer to form a crosslinked network structure. The polyethylene glycol diacrylate itself forms a network structure through UV curing, which intertwines with the network structure of the quaternized polymer, thereby forming a dual-crosslinked structure. In this invention, the dual-crosslinked structure improves the stability and strength of the coating, giving it durable anti-fog properties and wear resistance; furthermore, it forms a fine nanostructure coating, which can alter the light propagation path, reducing light reflection and scattering on the coating surface, thereby increasing transmittance. Therefore, the waterborne coating provided by this invention, after UV curing, has the advantages of durable anti-fog effect (achieving over 20 days of durable anti-fog), good wear resistance, and high light transmittance, making it a dual-crosslinked, wear-resistant, transparent, anti-fog coating. Attached Figure Description

[0020] Figure 1 XPS spectrum of the quaternary ammonium salt polymer prepared in Example 1;

[0021] Figure 2 The infrared spectrum of the quaternary ammonium salt polymer prepared in Example 1;

[0022] Figure 3 The NMR spectrum of the quaternary ammonium salt polymer prepared in Example 1;

[0023] Figure 4 Thermogravimetric curve of the quaternary ammonium salt polymer prepared in Example 1;

[0024] Figure 5 The anti-fog effect of the double crosslinked wear-resistant transparent anti-fog coating prepared in Example 1 of this invention was tested using the hot steam method.

[0025] Figure 6 The anti-fog effect of the double crosslinked wear-resistant transparent anti-fog coating prepared in Example 1 of this invention was tested using the hot and cold method.

[0026] Figure 7 This is a schematic diagram illustrating the effect of the double crosslinked wear-resistant transparent anti-fog coating prepared in Example 1 of the present invention applied to goggles;

[0027] Figure 8 This is a schematic diagram of the contact angle of the double crosslinked wear-resistant transparent anti-fog coating prepared in Example 1 of the present invention after being rubbed several times in a rubber-alcohol abrasion tester.

[0028] Figure 9The image shows the transmittance of the double crosslinked wear-resistant transparent anti-fog coating prepared in Example 1 of this invention.

[0029] Figure 10 The image shows the anti-fogging effect of the single crosslinked anti-fogging coating prepared in Comparative Example 1 of this invention, tested using the hot steam method.

[0030] Figure 11 The image shows the anti-fogging effect of the single crosslinked anti-fogging coating prepared in Comparative Example 2 of this invention, tested using the hot steam method. Detailed Implementation

[0031] This invention provides a quaternary ammonium salt polymer, prepared by a method comprising the following steps:

[0032] Dimethylaminoethyl methacrylate, acrylic acid, initiator and organic solvent were mixed and subjected to free radical polymerization to obtain the primary polymer;

[0033] The primary polymer, 1-bromoheptane, and an organic solvent are mixed and subjected to a quaternization reaction to obtain the quaternary ammonium salt polymer.

[0034] Unless otherwise specified, all raw materials involved in this invention are commercially available products well known to those skilled in the art.

[0035] This invention involves mixing dimethylaminoethyl methacrylate, acrylic acid, an initiator, and an organic solvent to undergo a free radical polymerization reaction to obtain a primary polymer. In this invention, the mass ratio of dimethylaminoethyl methacrylate to acrylic acid is preferably 8:1 to 11:1, more preferably 9:1 to 10:1. In this invention, the initiator is preferably azobisisobutyronitrile (AIB), and the mass of the initiator is preferably 1% of the total mass of dimethylaminoethyl methacrylate and acrylic acid. In this invention, the organic solvent is preferably o-xylene. This invention does not have specific requirements for the amount of organic solvent used, as long as it ensures the dissolution of the raw materials and the smooth progress of the reaction.

[0036] In this invention, the preferred method for mixing dimethylaminoethyl methacrylate, acrylic acid, initiator, and organic solvent is as follows: adding dimethylaminoethyl methacrylate, acrylic acid, and organic solvent into a reaction vessel and mixing to obtain a monomer solution; then adding an initiator to the monomer solution.

[0037] In this invention, the temperature of the free radical polymerization reaction is preferably 75–85°C, more preferably 80–85°C, and the time is preferably 10–13 h, more preferably 11–12 h; the free radical polymerization reaction is preferably carried out under stirring conditions. In this invention, the reaction formula for the free radical polymerization reaction is as follows:

[0038]

[0039] After the free radical polymerization reaction is completed, the present invention preferably precipitates the obtained reaction solution in n-hexane, and washes and dries the obtained solid product sequentially to obtain the primary polymer. In the present invention, the washing reagent used is preferably n-hexane, and the washing is preferably performed 3 times; the drying temperature is preferably 40°C, and the drying time is based on drying to constant weight.

[0040] After obtaining the primary polymer, the present invention mixes the primary polymer, 1-bromoheptane, and an organic solvent to carry out a quaternization reaction to obtain the quaternary ammonium salt polymer. In the present invention, the mass ratio of the primary polymer to 1-bromoheptane is preferably 1:1.4 to 1:1.7, more preferably 1:1.5 to 1:1.6. In the present invention, the organic solvent is preferably acetonitrile. The present invention does not have particular requirements on the amount of organic solvent used, as long as it ensures the dissolution of the primary polymer and 1-bromoheptane and the smooth progress of the reaction.

[0041] In this invention, the temperature of the quaternization reaction is preferably 75–85°C, more preferably 80°C, and the time is preferably 10–13 h, more preferably 12 h; the quaternization reaction is preferably carried out under stirring conditions. In this invention, the reaction formula for the quaternization reaction is as follows:

[0042]

[0043] After the quaternization reaction is completed, the present invention preferably removes the organic solvent by vacuum rotary evaporation of the obtained reaction solution to obtain a solid product; the solid product is washed with n-hexane to remove unreacted monomers and impurities, and then dried to obtain the quaternized polymer.

[0044] The quaternized polymer provided by this invention has a hydrophilic effect, is easily soluble in water, and can absorb water droplets condensed on the coating surface, thus giving it an anti-fogging effect.

[0045] This invention provides a double crosslinked wear-resistant transparent anti-fog waterborne coating, the components of which include a quaternized polymer, water, a trifunctional aziridine crosslinking agent, polyethylene glycol diacrylate, and a photoinitiator; the quaternized polymer is the quaternary ammonium salt polymer described in the above technical solution.

[0046] In this invention, the trifunctional aziridine crosslinking agent has CAS number 57116-45-7 and was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.; the photoinitiator preferably includes one or more of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2-hydroxy-2-methylphenylacetone, and benzophenone; the polyethylene glycol diacrylate has CAS number 26570-48-9, an average molecular weight of ~400, and was purchased from Shanghai Maclean Biochemical Technology Co., Ltd. The polyethylene glycol diacrylate contains two double bond end groups in its structure, which facilitates free radical polymerization under photoinitiation to form a crosslinked network structure. In this invention, the mass of the trifunctional aziridine crosslinking agent is preferably 15-22% of the mass of the quaternized polymer, more preferably 18-21%; the mass of the polyethylene glycol diacrylate is preferably 1.8-2.2% of the mass of the quaternized polymer, more preferably 2%; the mass of the photoinitiator is preferably 8-12% of the mass of the polyethylene glycol diacrylate, more preferably 10%; and the mass concentration of the double-crosslinked wear-resistant transparent anti-fog waterborne coating is preferably 10-20%, more preferably 14-16%.

[0047] In this invention, the dual-crosslinked wear-resistant transparent anti-fog waterborne coating is prepared by mixing its components. The preferred mixing method is as follows: dissolve the quaternized polymer in water, stir until homogeneous, add a trifunctional aziridine crosslinking agent, stir again until homogeneous, and then add polyethylene glycol diacrylate and a photoinitiator to obtain the dual-crosslinked wear-resistant transparent anti-fog waterborne coating. In this invention, the mixing can be carried out at room temperature.

[0048] The double crosslinked wear-resistant transparent anti-fog waterborne coating provided by this invention can be cured by ultraviolet light to obtain a transparent wear-resistant coating with durable anti-fog properties, which solves the problems of single performance and poor wear resistance of waterborne coatings; moreover, the preparation method is simple, environmentally friendly, and has almost no harm to human health.

[0049] This invention provides a double-crosslinked wear-resistant transparent anti-fog coating, which is obtained by applying the double-crosslinked wear-resistant transparent anti-fog water-based coating described in the above technical solution to the surface of a substrate and then curing it under ultraviolet light. This invention does not have special requirements for the substrate; appropriate substrates can be selected according to actual needs. In this embodiment, the substrate is preferably a hydrophilic substrate, which can be an optically transparent material of any shape and volume, such as glass, medical goggles, agricultural polyolefin greenhouse film, PET film, etc. Before coating, the substrate surface is preferably cleaned with deionized water and anhydrous ethanol, dried, and then subjected to plasma cleaning. The plasma cleaning time is preferably 3-5 minutes. In this invention, the coating method is preferably drop coating, blade coating, or spin coating; the coating should be uniform.

[0050] In this invention, the UV power for UV curing is preferably 800-1000W, more preferably 900W, and the curing time is preferably 20-40min, more preferably 30min. During the UV curing process, the aziridine crosslinking agent reacts with the carboxyl groups contained in the quaternized polymer to form a crosslinked network structure. The polyethylene glycol diacrylate itself forms a network structure through UV curing, which intertwines with the network structure of the quaternized polymer, thereby forming a double crosslinked structure.

[0051] This invention improves the stability and strength of the coating through a double crosslinking method, giving the coating durable anti-fogging properties and good wear resistance. It can achieve durable anti-fogging for more than 20 days and has the advantages of good biocompatibility, high light transmittance, and simple preparation method.

[0052] To further illustrate the present invention, the quaternary ammonium salt polymer, the double crosslinked wear-resistant transparent anti-fog waterborne coating and its coating provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of protection of the present invention.

[0053] Example 1

[0054] 40g of dimethylaminoethyl methacrylate monomer and 4g of acrylic acid monomer were dissolved in 44g of o-xylene, and 0.44g of azobisisobutyronitrile was added. The mixture was refluxed in an oil bath at 80℃ for 12h. After reflux, the mixture was precipitated with n-hexane and washed three times. The mixture was then dried in a vacuum drying oven at 40℃ to obtain the primary polymer.

[0055] 4 g of the primary polymer and 6.24 g of 1-bromoheptane were dissolved in 30 mL of acetonitrile and refluxed in an oil bath at 80 °C for 12 h. After reflux, the organic solvent was removed by vacuum rotary evaporation to obtain a solid product. Unreacted monomers and impurities were then removed by washing with n-hexane and dried under vacuum to obtain the quaternized polymer.

[0056] 1.2g of quaternized polymer was dissolved in water to prepare a 15% (w / w) solution. After stirring evenly, 0.236g of trifunctional aziridine crosslinking agent (CAS: 57116-45-7) was added. After stirring for 2 hours, 0.024g of polyethylene glycol diacrylate (CAS: 26570-48-9) and 0.0024g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone were added to obtain a wear-resistant, transparent, anti-fog waterborne coating.

[0057] The above-mentioned water-based coating was uniformly dripped onto the surface of the treated PET film and then placed in a 900W UV curing oven for 30 minutes to obtain a double crosslinked wear-resistant transparent anti-fog coating (coating thickness 2.5 micrometers).

[0058] Example 2

[0059] 40g of dimethylaminoethyl methacrylate monomer and 4g of acrylic acid monomer were dissolved in 44g of o-xylene, and 0.44g of azobisisobutyronitrile was added. The mixture was refluxed in an oil bath at 80℃ for 12h. After reflux, the mixture was precipitated with n-hexane and washed three times. The mixture was then dried in a vacuum drying oven at 40℃ to obtain the primary polymer.

[0060] 4 g of the primary polymer and 5.80 g of 1-bromoheptane were dissolved in 30 mL of acetonitrile and refluxed in an oil bath at 80 °C for 12 h. After reflux, the organic solvent was removed by vacuum rotary evaporation to obtain a solid product. Unreacted monomers and impurities were then removed by washing with n-hexane and dried under vacuum to obtain the quaternized polymer.

[0061] 1.2g of quaternized polymer was dissolved in water to prepare a 15% (w / w) solution. After stirring evenly, 0.236g of trifunctional aziridine crosslinking agent (CAS: 57116-45-7) was added. After stirring for 2 hours, 0.024g of polyethylene glycol diacrylate (CAS: 26570-48-9) and 0.0024g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone were added to obtain a wear-resistant, transparent, anti-fog waterborne coating.

[0062] The above-mentioned water-based coating was evenly dripped onto the surface of the treated PET film and then placed in a 900W UV curing oven for 30 minutes to obtain a double crosslinked wear-resistant transparent anti-fog coating.

[0063] Example 3

[0064] 40g of dimethylaminoethyl methacrylate monomer and 4g of acrylic acid monomer were dissolved in 44g of o-xylene, and 0.44g of azobisisobutyronitrile was added. The mixture was refluxed in an oil bath at 80℃ for 12h. After reflux, the mixture was precipitated with n-hexane and washed three times. The mixture was then dried in a vacuum drying oven at 40℃ to obtain the primary polymer.

[0065] 4 g of the primary polymer and 6.63 g of 1-bromoheptane were dissolved in 30 mL of acetonitrile and refluxed in an oil bath at 80 °C for 12 h. After reflux, the organic solvent was removed by vacuum rotary evaporation to obtain a solid product. Unreacted monomers and impurities were then removed by washing with n-hexane and dried under vacuum to obtain the quaternized polymer.

[0066] 1.2g of quaternized polymer was dissolved in water to prepare a 15% (w / w) solution. After stirring evenly, 0.236g of trifunctional aziridine crosslinking agent (CAS: 57116-45-7) was added. After stirring for 2 hours, 0.024g of polyethylene glycol diacrylate (CAS: 26570-48-9) and 0.0024g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone were added to obtain a wear-resistant, transparent, anti-fog waterborne coating.

[0067] The above-mentioned water-based coating was evenly dripped onto the surface of the treated PET film and then placed in a 900W UV curing oven for 30 minutes to obtain a double crosslinked wear-resistant transparent anti-fog coating.

[0068] Example 4

[0069] 45g of dimethylaminoethyl methacrylate monomer and 5g of acrylic acid monomer were dissolved in 50g of o-xylene, and 0.50g of azobisisobutyronitrile was added. The mixture was refluxed in an oil bath at 80℃ for 12h. After reflux, the mixture was precipitated with n-hexane and washed three times. The mixture was then dried in a vacuum drying oven at 40℃ to obtain the primary polymer.

[0070] 4 g of the primary polymer and 6.15 g of 1-bromoheptane were dissolved in 30 mL of acetonitrile and refluxed in an oil bath at 80 °C for 12 h. After reflux, the organic solvent was removed by vacuum rotary evaporation to obtain a solid product. Unreacted monomers and impurities were then removed by washing with n-hexane and dried under vacuum to obtain the quaternized polymer.

[0071] 1.2g of quaternized polymer was dissolved in water to prepare a 15% (w / w) solution. After stirring evenly, 0.236g of trifunctional aziridine crosslinking agent (CAS: 57116-45-7) was added. After stirring for 2 hours, 0.024g of polyethylene glycol diacrylate (CAS: 26570-48-9) and 0.0024g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone were added to obtain a wear-resistant, transparent, anti-fog waterborne coating.

[0072] The above-mentioned water-based coating was evenly dripped onto the surface of the treated PET film and then placed in a 900W UV curing oven for 30 minutes to obtain a double crosslinked wear-resistant transparent anti-fog coating.

[0073] Example 5

[0074] 40g of dimethylaminoethyl methacrylate monomer and 4g of acrylic acid monomer were dissolved in 44g of o-xylene, and 0.44g of azobisisobutyronitrile was added. The mixture was refluxed in an oil bath at 80℃ for 12h. After reflux, the mixture was precipitated with n-hexane and washed three times. The mixture was then dried in a vacuum drying oven at 40℃ to obtain the primary polymer.

[0075] 4 g of the primary polymer and 6.24 g of 1-bromoheptane were dissolved in 30 mL of acetonitrile and refluxed in an oil bath at 80 °C for 12 h. After reflux, the organic solvent was removed by vacuum rotary evaporation to obtain a solid product. Unreacted monomers and impurities were then removed by washing with n-hexane and dried under vacuum to obtain the quaternized polymer.

[0076] 1.2g of quaternized polymer was dissolved in water to prepare a 15% (w / w) solution. After stirring until homogeneous, 0.216g of trifunctional aziridine crosslinking agent (CAS: 57116-45-7) was added. After stirring for 2 hours, 0.024g of polyethylene glycol diacrylate (CAS: 26570-48-9) and 0.0024g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone were added to obtain a wear-resistant, transparent, anti-fog waterborne coating.

[0077] The above-mentioned water-based coating was evenly dripped onto the surface of the treated PET film and then placed in a 900W UV curing oven for 30 minutes to obtain a double crosslinked wear-resistant transparent anti-fog coating.

[0078] Example 6

[0079] 40g of dimethylaminoethyl methacrylate monomer and 4g of acrylic acid monomer were dissolved in 44g of o-xylene, and 0.44g of azobisisobutyronitrile was added. The mixture was refluxed in an oil bath at 80℃ for 12h. After reflux, the mixture was precipitated with n-hexane and washed three times. The mixture was then dried in a vacuum drying oven at 40℃ to obtain the primary polymer.

[0080] 4 g of the primary polymer and 6.24 g of 1-bromoheptane were dissolved in 30 mL of acetonitrile and refluxed in an oil bath at 80 °C for 12 h. After reflux, the organic solvent was removed by vacuum rotary evaporation to obtain a solid product. Unreacted monomers and impurities were then removed by washing with n-hexane and dried under vacuum to obtain the quaternized polymer.

[0081] 1.2g of quaternized polymer was dissolved in water to prepare a 14% (w / w) solution. After stirring until homogeneous, 0.216g of trifunctional aziridine crosslinking agent (CAS: 57116-45-7) was added. After stirring for 2 hours, 0.024g of polyethylene glycol diacrylate (CAS: 26570-48-9) and 0.0024g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone were added to obtain a wear-resistant, transparent, anti-fog waterborne coating.

[0082] The above-mentioned water-based coating was evenly dripped onto the surface of the treated PET film and then placed in a 900W UV curing oven for 30 minutes to obtain a double crosslinked wear-resistant transparent anti-fog coating.

[0083] Comparative Example 1

[0084] The preparation method is basically the same as that in Example 1, except that no trifunctional aziridine crosslinking agent is added during preparation.

[0085] Comparative Example 2

[0086] The preparation method is basically the same as that in Example 1, except that polyethylene glycol diacrylate and photoinitiator 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone are not added during preparation, and the curing method is thermosetting.

[0087] Figures 1-4 The following are, in order, the XPS, IR, NMR, and thermogravimetric spectra of the quaternary ammonium salt polymer prepared in Example 1. Figure 1 The presence of N and Br peaks in the XPS spectrum indicates that 1-bromoheptane successfully protonated the tertiary amine groups in the copolymer. Figure 2 2776 cm⁻¹ in the infrared spectrum -1 The characteristic peak at the location reveals the stretching vibration of CH in the quaternary ammonium group, indicating the introduction of the quaternary ammonium group. Figure 3 Analysis of the groups corresponding to the chemical shift further confirmed the successful preparation of the quaternized polymer. Figures 1-3 This demonstrates the successful preparation of quaternized polymers. Figure 4 The thermogravimetric curves show that quaternization results in better thermal stability.

[0088] The anti-fogging effect of the double crosslinked wear-resistant transparent anti-fogging coating prepared in the example was tested by the hot steam method. The test method was to place the prepared double crosslinked wear-resistant transparent anti-fogging coating above a water bath at 60°C and record the fogging phenomenon on its surface with a camera. Figure 5 The image shows the anti-fogging effect of the double-crosslinked wear-resistant transparent anti-fogging coating prepared in Example 1, tested using the hot steam method. Figure 5 It can be seen that the double crosslinked wear-resistant transparent anti-fog coating prepared in Example 1 can maintain the anti-fog effect for more than 20 days.

[0089] The anti-fogging effect of the double crosslinked wear-resistant transparent anti-fogging coating prepared in the example was tested using the hot and cold method. The test method was to place the prepared double crosslinked wear-resistant transparent anti-fogging coating in a refrigerator at -20°C for 30 minutes, and then record the fogging phenomenon on the coating surface with a camera after taking it out. Figure 6 The image shows the anti-fogging effect of the double-crosslinked wear-resistant transparent anti-fogging coating prepared in Example 1, tested using the warm and cold method. Figure 6 It can be seen that the double crosslinked wear-resistant transparent anti-fog coating prepared in Example 1 still maintains its transparency after being taken out of the refrigerator, and the surface does not fog up, indicating that its anti-fog effect is good.

[0090] Figure 7 This is a schematic diagram illustrating the effect of the double-crosslinked wear-resistant transparent anti-fog coating prepared in Example 1 of the present invention applied to goggles. Figure 7 It can be seen that when moving from the cold outdoors to the warm indoors, the goggles with the double cross-linked wear-resistant transparent anti-fog coating maintain their high transparency and do not produce fog, while the goggles without the coating have significantly reduced transparency and fog can be clearly seen on the surface.

[0091] Figure 8 This is a schematic diagram showing the contact angle of the double-crosslinked wear-resistant transparent anti-fog coating prepared in Example 1 of the present invention after several cycles of friction in a rubber-alcohol abrasion tester. The friction pair in the abrasion test was a polyester fabric, with a load of 100g. Figure 8 It can be seen that after 12,000 cycles of reciprocating friction, the contact angle of the coating surface only decreased slightly, indicating that the prepared double crosslinked wear-resistant transparent anti-fog coating has excellent wear resistance.

[0092] Figure 9 This is a transmittance effect diagram of the double-crosslinked wear-resistant transparent anti-fog coating prepared in Example 1 of the present invention. Figure 9 It can be seen that the transmittance of the coating is 84-89%, while that of the blank PET is 81-87%. The transmittance of the coating is slightly higher than that of the blank PET, indicating that the prepared double crosslinked wear-resistant transparent anti-fog coating has a certain anti-reflective effect.

[0093] Tests showed that the double crosslinked wear-resistant transparent anti-fog coatings prepared in Examples 2-6 had similar anti-fog, wear-resistant and light-transmitting properties as those in Example 1.

[0094] Figure 10 The image shows the anti-fogging effect of the single crosslinked anti-fogging coating prepared in Comparative Example 1 of this invention, tested using the hot steam method. Figure 11 This image shows the anti-fogging effect of the single-crosslinked anti-fogging coating prepared in Comparative Example 2 of this invention, tested using the hot steam method. Figure 10 and Figure 11 It can be seen that the coating crosslinked with only polyethylene glycol diacrylate can only maintain the anti-fog effect for about 24 hours, while the coating crosslinked with only trifunctional aziridine crosslinking agent can only maintain the anti-fog effect for about 40 hours.

[0095] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A double-crosslinked, wear-resistant, transparent, anti-fog water-based coating, characterized in that, The components are a quaternized polymer, water, a trifunctional aziridine crosslinking agent, polyethylene glycol diacrylate, and a photoinitiator; the quaternized polymer is a quaternary ammonium salt polymer, which is prepared by a method comprising the following steps: Dimethylaminoethyl methacrylate, acrylic acid, an initiator, and an organic solvent are mixed and subjected to a free radical polymerization reaction to obtain a primary polymer; the mass ratio of dimethylaminoethyl methacrylate to acrylic acid is 8:1 to 11:1, the temperature of the free radical polymerization reaction is 75 to 85°C, and the time is 10 to 13 hours. The primary polymer, 1-bromoheptane, and an organic solvent are mixed and subjected to a quaternization reaction to obtain the quaternary ammonium salt polymer; the mass ratio of the primary polymer to 1-bromoheptane is 1:1.4 to 1:1.7, the temperature of the quaternization reaction is 75 to 85°C, and the time is 10 to 13 hours. The mass of the trifunctional aziridine crosslinking agent is 15-22% of the mass of the quaternized polymer, and the mass of the polyethylene glycol diacrylate is 1.8-2.2% of the mass of the quaternized polymer.

2. The double-crosslinked wear-resistant transparent anti-fog water-based coating according to claim 1, characterized in that, The photoinitiator includes one or more of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2-hydroxy-2-methylphenylacetone, and benzophenone.

3. The double-crosslinked wear-resistant transparent anti-fog water-based coating according to claim 1 or 2, characterized in that, The photoinitiator has a mass of 8-12% of the mass of polyethylene glycol diacrylate; the double crosslinked wear-resistant transparent anti-fog waterborne coating has a solid content of 10-20 wt%.

4. A double-crosslinked wear-resistant transparent anti-fog coating, characterized in that, The coating is obtained by applying the double crosslinked wear-resistant transparent anti-fog water-based coating as described in any one of claims 1 to 3 to the surface of a substrate and then curing it under ultraviolet light.

5. The double crosslinked wear-resistant transparent anti-fog coating according to claim 4, characterized in that, The UV power for UV curing is 800~1000W, and the curing time is 20~40min.

Images