An anti-fog, antibacterial, and antistatic coating, its preparation method, and its application.

Abstract

This invention provides an anti-fogging, antibacterial, and antistatic coating, its preparation method, and its application. The anti-fogging, antibacterial, and antistatic coating comprises a substrate layer, an antistatic primer layer, and an anti-fogging and antibacterial coating. The substrate layer is thermoplastic polyurethane, polyethylene terephthalate, or cellulose triacetate. The antistatic primer layer comprises a dual-curing prepolymer, a reactive diluent, a first photoinitiator, a thermal initiator, an antistatic agent, and a first solvent. The anti-fogging and antibacterial coating comprises an allyl alkyl imidazole bromide prepolymer, modified inorganic particles, a hydrophilic UV prepolymer, a second photoinitiator, and a second solvent. It is obtained by preparing an antistatic coating liquid, an anti-fogging and antibacterial coating liquid, an antistatic primer layer, and an anti-fogging, antibacterial, and antistatic coating. The anti-fogging, antibacterial, and antistatic coating prepared by this invention can be used in the preparation of mirror protective layers and has good anti-fogging, antibacterial, and antistatic properties.

Description

Technical Field

[0001] This invention belongs to the field of functional coating technology, specifically relating to an anti-fogging, antibacterial, and antistatic coating, its preparation method, and its application. Background Technology

[0002] With the rise of various electronic products, the number of people wearing glasses is increasing daily, and fogging of glasses has become a major concern. Furthermore, glasses are prone to harboring pathogenic bacteria such as E. coli and Staphylococcus aureus during wear, affecting people's health. To solve this problem, anti-fogging agents are typically sprayed onto the lens or an anti-fogging film is applied. Anti-fogging agents mainly reduce the surface tension of the lens by spraying a surfactant onto it, allowing water droplets to form a uniform water film. However, this method has a short anti-fogging time and is not scratch-resistant. Anti-fogging films are prepared in two ways: one is by coating a polyester substrate to form a superhydrophobic coating, where water droplets fall off under their own weight to achieve an anti-fogging effect. This method is mainly effective for strong fog and large water droplets; the other is by coating a polyester substrate to form a superhydrophilic coating, with the same principle as anti-fogging agents.

[0003] Neither anti-fogging agents nor anti-fogging films possess antibacterial properties. Furthermore, due to static electricity during manufacturing or use, they attract dust and contaminants, failing to achieve the desired anti-fogging effect (anti-fogging time > 30 min) and antibacterial effect (E. coli antibacterial rate > 95%). They also lack antistatic properties (surface resistance value 10). 6-9 This greatly limits the use of functional coatings in the field of mirror protection. Summary of the Invention

[0004] The problem to be solved by the present invention is to provide an anti-fog, antibacterial, and antistatic coating, its preparation method, and its application, so as to solve the technical problem of poor anti-fog film antibacterial and antistatic effects.

[0005] The technical solution adopted to solve the technical problem is to provide an anti-fog, antibacterial, and antistatic coating, which consists of a substrate layer, an antistatic primer layer, and an anti-fog and antibacterial coating layer from bottom to top. The substrate layer is made of thermoplastic polyurethane, polyethylene terephthalate, or cellulose triacetate. The antistatic primer layer includes the following raw materials in parts by weight: 5-15 parts of a dual-curing prepolymer, 7.5-22.5 parts of an active diluent, 1-5 parts of a first photoinitiator, 1-5 parts of a thermal initiator, 0.2-0.8 parts of an antistatic agent, and 51.7-85.3 parts of a first solvent. The anti-fog and antibacterial coating includes the following raw materials in parts by weight: 15-20 parts of an allyl alkyl imidazole bromide prepolymer, 5-10 parts of modified inorganic particles, 30-40 parts of a hydrophilic UV prepolymer, 1-5 parts of a second photoinitiator, and 25-49 parts of a second solvent.

[0006] Preferably, the substrate layer is made of thermoplastic polyurethane; the antistatic primer layer comprises the following raw materials in parts by weight: 12 parts of dual-curing prepolymer, 20 parts of reactive diluent, 3 parts of first photoinitiator, 3 parts of thermal initiator, 0.5 parts of antistatic agent and 61.5 parts of first solvent; the antifogging and antibacterial coating comprises the following raw materials in parts by weight: 15 parts of allyl alkyl imidazole bromide salt prepolymer, 5 parts of modified inorganic particles, 30 parts of hydrophilic UV prepolymer, 5 parts of second photoinitiator and 45 parts of second solvent.

[0007] Preferably, the dual-cured prepolymer is an aliphatic polyurethane acrylate containing -NCO groups; the reactive diluent is pentaerythritol triacrylate or trimethylolpropane triacrylate; the first photoinitiator and the second photoinitiator are 1-hydroxy-cyclohexylbenzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, liquid α-hydroxy ketone composite photoinitiator, or methyl benzoylformate, respectively; the thermal initiator is benzoyl peroxide or dilauryl peroxide; the antistatic agent is hexadecyl dimethyl quaternary ammonium nitrate; and the first solvent and the second solvent are one or a mixture of two of ethylene glycol monoethyl ether, propylene glycol methyl ether, isopropanol, and N,N-dimethylformamide in a 1:1 mass ratio.

[0008] Preferably, the allyl alkyl imidazolium bromide prepolymer is prepared by the following steps:

[0009] 1-Allylimidazolium and bromoalkane are added to a container in a molar ratio of 1:2, followed by the addition of an organic solvent. The mixture is stirred at 60°C for 24 hours under an inert atmosphere. After cooling to room temperature, it is rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allylalkylimidazolium salt monomer. The allylalkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester are mixed in a molar ratio of 1:1 to 2:1 to 2:5, dissolved in a solvent, and then 0.5 to 1 wt% of a photoinitiator containing pure solids is added. After irradiation with ultraviolet light, the product is obtained.

[0010] More preferably, the bromoalkane is bromooctane, bromodecane, bromododecane, or bromotetradecane.

[0011] Preferably, the modified inorganic particles are modified hollow titanium dioxide with a surface containing fluorinated siloxanes; the fluorinated siloxanes are tridecafluorooctyltriethoxysilane or heptadecafluorodecyltriethoxysilane; the modified inorganic particles are prepared through the following steps:

[0012] Hollow titanium dioxide and hydrogen peroxide were mixed at a mass ratio of 1:3, sonicated for 20–40 min, and refluxed at 75–85 °C for 3–5 h. After filtration, the mixture was washed with water and then vacuum dried at 70–90 °C to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:1–3 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 15–25 min. Then, a fluorosiloxane was added, and the mixture was magnetically stirred at 55–65 °C for 2.5–3.5 h. After filtration, the mixture was washed with water and then dried at 70–90 °C to constant weight to obtain the final product.

[0013] Preferably, the hydrophilic UV prepolymer is Changxing DR-W470, Changxing DR-W450, Bayer UV LS2282, Bayer UV LS2317, BASF LR8949 or BASF LR9005.

[0014] Preferably, the thickness of the substrate layer is 25–250 μm; the thickness of the antistatic primer layer is 90–120 nm; and the thickness of the anti-fog and antibacterial coating is 2–5 μm.

[0015] The present invention also provides a method for preparing the above-mentioned anti-fogging, antibacterial, and antistatic coating, comprising the following steps:

[0016] (1) Mix the first solvent, the dual-cured prepolymer and the reactive diluent, stir at 500-800 r / min for 30 min, add the antistatic agent, stir at 500-800 r / min for 5 min, add the first photoinitiator, stir at 500-800 r / min for 5 min, add the thermal initiator, stir at 500-800 r / min for 5 min, and finally stir at 800-1000 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid.

[0017] (2) Mix the second solvent, allyl alkyl imidazole bromide prepolymer and hydrophilic UV prepolymer, stir at 500-800 r / min for 30 min, add modified inorganic particles and stir at 800-1000 r / min for 30 min, then add the second photoinitiator and stir at 800-1000 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fog antibacterial coating liquid;

[0018] (3) Apply an antistatic coating liquid to the substrate layer using a micro-gravure coating process, dry at 100℃ for 1 min, and then apply 500 mJ / cm 2 The antistatic base coating is obtained by irradiation with ultraviolet light;

[0019] (4) Apply an anti-fogging and antibacterial coating liquid to the surface of the antistatic primer using a micro-recessed, slit, or doctor blade coating process, dry at 90°C for 2 minutes, and then apply 500 mJ / cm² of coating solution. 2 When exposed to ultraviolet light, an anti-fog, antibacterial, and antistatic coating is obtained.

[0020] The present invention also provides the application of the above-mentioned anti-fog, antibacterial and antistatic coating in the preparation of a mirror protective layer.

[0021] The present invention has the following beneficial effects:

[0022] (1) The anti-fogging, antibacterial, and antistatic coating prepared by this invention has an anti-fogging time of >30 min, an antibacterial rate of >95% against Escherichia coli, and a surface impedance of up to 10. 6-9 Its hardness can reach 3H;

[0023] (2) The anti-fogging, antibacterial and antistatic coating prepared by the present invention has anti-fogging properties as well as antibacterial and antistatic properties.

[0024] (3) The anti-fog, antibacterial and antistatic coating prepared by the present invention has a simple structure, is easy to prepare, and has great economic benefits and market prospects. Attached Figure Description

[0025] Figure 1 This is a structural diagram of the anti-fog, antibacterial, and antistatic coating. Detailed Implementation

[0026] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0027] Example 1

[0028] An anti-fogging, antibacterial, and antistatic coating comprises, from bottom to top, a substrate layer with a thickness of 120 μm, an antistatic base layer with a thickness of 100 nm, and an anti-fogging and antibacterial coating with a thickness of 3 μm. The substrate layer is made of thermoplastic polyurethane. The antistatic base layer comprises the following raw materials in parts by weight: 12 parts of aliphatic polyurethane acrylate containing -NCO groups (Bayer UA). The antifog and antibacterial coating comprises the following raw materials in parts by weight: VPLS2337), 20 parts pentaerythritol triacrylate (Sartoma SR444), 3 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), 3 parts benzoyl peroxide (Merck), 0.5 parts hexadecyl dimethyl quaternary ammonium nitrate, and 61.5 parts of a mixed solvent, which is obtained by mixing 30.75 parts propylene glycol methyl ether and 30.75 parts isopropanol; the antifog and antibacterial coating comprises the following raw materials in parts by weight: 15 parts allyl alkyl imidazole bromide prepolymer, 5 parts heptadecafluorodecyltriethoxysilane modified hollow titanium dioxide particles, 30 parts BASF LR8949, 5 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), and 45 parts of a mixed solvent, which is obtained by mixing 22.5 parts propylene glycol methyl ether and 22.5 parts isopropanol.

[0029] The allyl alkyl imidazolium bromide prepolymer is prepared through the following steps:

[0030] 1-Allylimidazolium and bromododecane were added to a container in a molar ratio of 1:2, followed by 10 parts by mass of acetonitrile. The mixture was stirred at 60°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allylalkylimidazolium salt monomer. The allylalkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester were mixed in a molar ratio of 1:2:1:5, dissolved in 30 parts by mass of propylene glycol methyl ether, and then 0.5 wt% of pure solid 1-hydroxy-cyclohexyl benzophenone (BASF) was added. The mixture was then irradiated with ultraviolet light to obtain the final product.

[0031] The heptadecanyltriethoxysilane-modified hollow titanium dioxide particles were prepared through the following steps:

[0032] Hollow titanium dioxide was mixed with hydrogen peroxide at a mass ratio of 1:3, sonicated for 30 min, refluxed at 80°C for 4 h, filtered, washed with water, and then vacuum dried at 80°C to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:2 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 20 min. Then, 1 wt% of heptadecafluorodecyltriethoxysilane was added, and the mixture was magnetically stirred at 60°C for 3 h. After filtration, washing with water, and drying at 80°C to constant weight, the final product was obtained.

[0033] The anti-fog, antibacterial, and antistatic coating in this embodiment is prepared through the following steps:

[0034] (1) Mix propylene glycol methyl ether and isopropanol, aliphatic polyurethane acrylate containing -NCO group (Bayer UAVP LS2337) and pentaerythritol triacrylate (Sartoma SR444), stir at 650 r / min for 30 min, add hexadecyl dimethyl quaternary ammonium nitrate, stir at 650 r / min for 5 min, add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), stir at 650 r / min for 5 min, add benzoyl peroxide (Merck), stir at 650 r / min for 5 min, and finally stir at 900 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid.

[0035] (2) Mix propylene glycol methyl ether and isopropanol, allyl alkyl imidazole bromide salt prepolymer and BASF LR8949, stir at 650 r / min for 30 min, add heptadecanodecyltriethoxysilane modified hollow titanium dioxide particles and stir at 900 r / min for 30 min, then add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF) and stir at 900 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fogging antibacterial coating liquid;

[0036] (3) Apply an antistatic coating liquid to the substrate layer using a micro-gravure coating process, dry at 100℃ for 1 min, and then apply 500 mJ / cm 2 The antistatic base coating is obtained by irradiation with ultraviolet light;

[0037] (4) Apply an anti-fogging and antibacterial coating liquid to the surface of the antistatic primer using a micro-recessed, slit, or doctor blade coating process, dry at 90°C for 2 minutes, and then apply 500 mJ / cm² of coating solution. 2 When exposed to ultraviolet light, an anti-fog, antibacterial, and antistatic coating is obtained.

[0038] Example 2

[0039] An anti-fogging, antibacterial, and antistatic coating comprises, from bottom to top, a substrate layer with a thickness of 120 μm, an antistatic base layer with a thickness of 100 nm, and an anti-fogging and antibacterial coating with a thickness of 3 μm. The substrate layer is made of polyethylene terephthalate. The antistatic base layer comprises the following raw materials in parts by weight: 12 parts of aliphatic polyurethane acrylate containing -NCO groups (Bayer UA VP). The antifog and antibacterial coating comprises the following raw materials in parts by weight: 15 parts allyl alkyl imidazole bromide prepolymer, 5 parts heptadecanyltriethoxysilane modified hollow titanium dioxide particles, 30 parts BASF LR8949, 5 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), and 45 parts mixed solvent, which is obtained by mixing 22.5 parts propylene glycol methyl ether and 22.5 parts isopropanol.

[0040] The allyl alkyl imidazolium bromide prepolymer is prepared through the following steps:

[0041] 1-Allylimidazolium and bromododecane were added to a container in a molar ratio of 1:2, followed by 10 parts by mass of acetonitrile. The mixture was stirred at 60°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allylalkylimidazolium salt monomer. The allylalkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester were mixed in a molar ratio of 1:2:1:5, dissolved in 30 parts by mass of propylene glycol methyl ether, and then 0.5 wt% of pure solid 1-hydroxy-cyclohexyl benzophenone (BASF) was added. The mixture was then irradiated with ultraviolet light to obtain the final product.

[0042] The heptadecanyltriethoxysilane-modified hollow titanium dioxide particles were prepared through the following steps:

[0043] Hollow titanium dioxide was mixed with hydrogen peroxide at a mass ratio of 1:3, sonicated for 30 min, refluxed at 80°C for 4 h, filtered, washed with water, and then vacuum dried at 80°C to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:2 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 20 min. Then, 1 wt% of heptadecafluorodecyltriethoxysilane was added, and the mixture was magnetically stirred at 60°C for 3 h. After filtration, washing with water, and drying at 80°C to constant weight, the final product was obtained.

[0044] The anti-fog, antibacterial, and antistatic coating in this embodiment is prepared through the following steps:

[0045] (1) Mix propylene glycol methyl ether and isopropanol, aliphatic polyurethane acrylate containing -NCO group (Bayer UAVP LS2337) and pentaerythritol triacrylate (Sartoma SR444), stir at 650 r / min for 30 min, add hexadecyl dimethyl quaternary ammonium nitrate, stir at 650 r / min for 5 min, add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), stir at 650 r / min for 5 min, add benzoyl peroxide (Merck), stir at 650 r / min for 5 min, and finally stir at 900 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid.

[0046] (2) Mix propylene glycol methyl ether and isopropanol, allyl alkyl imidazole bromide salt prepolymer and BASF LR8949, stir at 650 r / min for 30 min, add heptadecanodecyltriethoxysilane modified hollow titanium dioxide particles and stir at 900 r / min for 30 min, then add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF) and stir at 900 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fogging antibacterial coating liquid;

[0047] (3) Apply an antistatic coating liquid to the substrate layer using a micro-gravure coating process, dry at 100℃ for 1 min, and then apply 500 mJ / cm 2 The antistatic base coating is obtained by irradiation with ultraviolet light;

[0048] (4) Apply an anti-fogging and antibacterial coating liquid to the surface of the antistatic primer using a micro-recessed, slit, or doctor blade coating process, dry at 90°C for 2 minutes, and then apply 500 mJ / cm² of coating solution. 2 When exposed to ultraviolet light, an anti-fog, antibacterial, and antistatic coating is obtained.

[0049] Example 3

[0050] An anti-fogging, antibacterial, and antistatic coating comprises, from bottom to top, a substrate layer with a thickness of 120 μm, an antistatic base layer with a thickness of 100 nm, and an anti-fogging and antibacterial coating with a thickness of 3 μm. The substrate layer is made of cellulose triacetate. The antistatic base layer comprises the following raw materials in parts by weight: 12 parts of aliphatic polyurethane acrylate containing -NCO groups (Bayer UA). The antifog and antibacterial coating comprises the following raw materials in parts by weight: VPLS2337), 20 parts pentaerythritol triacrylate (Sartoma SR444), 3 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), 3 parts benzoyl peroxide (Merck), 0.5 parts hexadecyl dimethyl quaternary ammonium nitrate, and 61.5 parts of a mixed solvent, which is obtained by mixing 30.75 parts propylene glycol methyl ether and 30.75 parts isopropanol; the antifog and antibacterial coating comprises the following raw materials in parts by weight: 15 parts allyl alkyl imidazole bromide prepolymer, 5 parts heptadecafluorodecyltriethoxysilane modified hollow titanium dioxide particles, 30 parts BASF LR8949, 5 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), and 45 parts of a mixed solvent, which is obtained by mixing 22.5 parts propylene glycol methyl ether and 22.5 parts isopropanol.

[0051] The allyl alkyl imidazolium bromide prepolymer is prepared through the following steps:

[0052] 1-Allylimidazolium and bromododecane were added to a container in a molar ratio of 1:2, followed by 10 parts by mass of acetonitrile. The mixture was stirred at 60°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allylalkylimidazolium salt monomer. The allylalkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester were mixed in a molar ratio of 1:2:1:5, dissolved in 30 parts by mass of propylene glycol methyl ether, and then 0.5 wt% of pure solid 1-hydroxy-cyclohexyl benzophenone (BASF) was added. The mixture was then irradiated with ultraviolet light to obtain the final product.

[0053] The heptadecanyltriethoxysilane-modified hollow titanium dioxide particles were prepared through the following steps:

[0054] Hollow titanium dioxide was mixed with hydrogen peroxide at a mass ratio of 1:3, sonicated for 30 min, refluxed at 80°C for 4 h, filtered, washed with water, and then vacuum dried at 80°C to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:2 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 20 min. Then, 1 wt% of heptadecafluorodecyltriethoxysilane was added, and the mixture was magnetically stirred at 60°C for 3 h. After filtration, washing with water, and drying at 80°C to constant weight, the final product was obtained.

[0055] The anti-fog, antibacterial, and antistatic coating in this embodiment is prepared through the following steps:

[0056] (1) Mix propylene glycol methyl ether and isopropanol, aliphatic polyurethane acrylate containing -NCO group (Bayer UAVP LS2337) and pentaerythritol triacrylate (Sartoma SR444), stir at 650 r / min for 30 min, add hexadecyl dimethyl quaternary ammonium nitrate, stir at 650 r / min for 5 min, add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), stir at 650 r / min for 5 min, add benzoyl peroxide (Merck), stir at 650 r / min for 5 min, and finally stir at 900 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid.

[0057] (2) Mix propylene glycol methyl ether and isopropanol, allyl alkyl imidazole bromide salt prepolymer and BASF LR8949, stir at 650 r / min for 30 min, add heptadecanodecyltriethoxysilane modified hollow titanium dioxide particles and stir at 900 r / min for 30 min, then add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF) and stir at 900 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fogging antibacterial coating liquid;

[0058] (3) Apply an antistatic coating liquid to the substrate layer using a micro-gravure coating process, dry at 100℃ for 1 min, and then apply 500 mJ / cm 2 The antistatic base coating is obtained by irradiation with ultraviolet light;

[0059] (4) Apply an anti-fogging and antibacterial coating liquid to the surface of the antistatic primer using a micro-recessed, slit, or doctor blade coating process, dry at 90°C for 2 minutes, and then apply 500 mJ / cm² of coating solution. 2 When exposed to ultraviolet light, an anti-fog, antibacterial, and antistatic coating is obtained.

[0060] Example 4

[0061] An anti-fogging, antibacterial, and antistatic coating comprises, from bottom to top, a substrate layer with a thickness of 120 μm, an antistatic base layer with a thickness of 100 nm, and an anti-fogging and antibacterial coating with a thickness of 3 μm. The substrate layer is made of thermoplastic polyurethane. The antistatic base layer comprises the following raw materials in parts by weight: 12 parts of aliphatic polyurethane acrylate containing -NCO groups (Bayer UA). The antifog and antibacterial coating comprises the following raw materials in parts by weight: VPLS2396), 20 parts pentaerythritol triacrylate (Sartoma SR444), 3 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), 3 parts benzoyl peroxide (Merck), 0.5 parts hexadecyl dimethyl quaternary ammonium nitrate, and 61.5 parts of a mixed solvent, which is obtained by mixing 30.75 parts propylene glycol methyl ether and 30.75 parts isopropanol; the antifog and antibacterial coating comprises the following raw materials in parts by weight: 15 parts allyl alkyl imidazole bromide prepolymer, 5 parts heptadecafluorodecyltriethoxysilane modified hollow titanium dioxide particles, 30 parts BASF LR8949, 5 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), and 45 parts of a mixed solvent, which is obtained by mixing 22.5 parts propylene glycol methyl ether and 22.5 parts isopropanol.

[0062] The allyl alkyl imidazolium bromide prepolymer is prepared through the following steps:

[0063] 1-Allylimidazolium and bromododecane were added to a container in a molar ratio of 1:2, followed by 10 parts by mass of acetonitrile. The mixture was stirred at 60°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allylalkylimidazolium salt monomer. The allylalkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester were mixed in a molar ratio of 1:2:1:5, dissolved in 30 parts by mass of propylene glycol methyl ether, and then 0.5 wt% of pure solid 1-hydroxy-cyclohexyl benzophenone (BASF) was added. The mixture was then irradiated with ultraviolet light to obtain the final product.

[0064] The heptadecanyltriethoxysilane-modified hollow titanium dioxide particles were prepared through the following steps:

[0065] Hollow titanium dioxide was mixed with hydrogen peroxide at a mass ratio of 1:3, sonicated for 30 min, refluxed at 80°C for 4 h, filtered, washed with water, and then vacuum dried at 80°C to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:2 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 20 min. Then, 1 wt% of heptadecafluorodecyltriethoxysilane was added, and the mixture was magnetically stirred at 60°C for 3 h. After filtration, washing with water, and drying at 80°C to constant weight, the final product was obtained.

[0066] The anti-fog, antibacterial, and antistatic coating in this embodiment is prepared through the following steps:

[0067] (1) Mix propylene glycol methyl ether and isopropanol, aliphatic polyurethane acrylate containing -NCO group (Bayer UAVP LS2396) and pentaerythritol triacrylate (Sartoma SR444), stir at 650 r / min for 30 min, add hexadecyl dimethyl quaternary ammonium nitrate, stir at 650 r / min for 5 min, add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), stir at 650 r / min for 5 min, add benzoyl peroxide (Merck), stir at 650 r / min for 5 min, and finally stir at 900 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid.

[0068] (2) Mix propylene glycol methyl ether and isopropanol, allyl alkyl imidazole bromide salt prepolymer and BASF LR8949, stir at 650 r / min for 30 min, add heptadecanodecyltriethoxysilane modified hollow titanium dioxide particles and stir at 900 r / min for 30 min, then add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF) and stir at 900 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fogging antibacterial coating liquid;

[0069] (3) Apply an antistatic coating liquid to the substrate layer using a micro-gravure coating process, dry at 100℃ for 1 min, and then apply 500 mJ / cm 2 The antistatic base coating is obtained by irradiation with ultraviolet light;

[0070] (4) Apply an anti-fogging and antibacterial coating liquid to the surface of the antistatic primer using a micro-recessed, slit, or doctor blade coating process, dry at 90°C for 2 minutes, and then apply 500 mJ / cm² of coating solution. 2 When exposed to ultraviolet light, an anti-fog, antibacterial, and antistatic coating is obtained.

[0071] Example 5

[0072] An anti-fogging, antibacterial, and antistatic coating comprises, from bottom to top, a substrate layer with a thickness of 120 μm, an antistatic base layer with a thickness of 100 nm, and an anti-fogging and antibacterial coating with a thickness of 3 μm. The substrate layer is made of thermoplastic polyurethane. The antistatic base layer comprises the following raw materials in parts by weight: 12 parts of aliphatic polyurethane acrylate containing -NCO groups (Bayer UA). The anti-fog and antibacterial coating comprises the following raw materials in parts by weight: 15 parts of allyl alkyl imidazole bromide prepolymer, 5 parts of heptadecanyltriethoxysilane modified hollow titanium dioxide particles, 30 parts of BASF LR8949, 5 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), and 45 parts of mixed solvent, which is obtained by mixing 22.5 parts of propylene glycol methyl ether and 22.5 parts of isopropanol.

[0073] The allyl alkyl imidazolium bromide prepolymer is prepared through the following steps:

[0074] 1-Allylimidazolium and bromododecane were added to a container in a molar ratio of 1:2, followed by 10 parts by mass of acetonitrile. The mixture was stirred at 60°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allylalkylimidazolium salt monomer. The allylalkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester were mixed in a molar ratio of 1:2:1:5, dissolved in 30 parts by mass of propylene glycol methyl ether, and then 0.5 wt% of pure solid 1-hydroxy-cyclohexyl benzophenone (BASF) was added. The mixture was then irradiated with ultraviolet light to obtain the final product.

[0075] The heptadecanyltriethoxysilane-modified hollow titanium dioxide particles were prepared through the following steps:

[0076] Hollow titanium dioxide was mixed with hydrogen peroxide at a mass ratio of 1:3, sonicated for 30 min, refluxed at 80°C for 4 h, filtered, washed with water, and then vacuum dried at 80°C to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:2 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 20 min. Then, 1 wt% of heptadecafluorodecyltriethoxysilane was added, and the mixture was magnetically stirred at 60°C for 3 h. After filtration, washing with water, and drying at 80°C to constant weight, the final product was obtained.

[0077] The anti-fog, antibacterial, and antistatic coating in this embodiment is prepared through the following steps:

[0078] (1) Mix propylene glycol methyl ether and isopropanol, aliphatic polyurethane acrylate containing -NCO group (Bayer UAXP 2510) and pentaerythritol triacrylate (Sartoma SR444), stir at 650 r / min for 30 min, add hexadecyl dimethyl quaternary ammonium nitrate, stir at 650 r / min for 5 min, add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), stir at 650 r / min for 5 min, add benzoyl peroxide (Merck), stir at 650 r / min for 5 min, and finally stir at 900 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid.

[0079] (2) Mix propylene glycol methyl ether and isopropanol, allyl alkyl imidazole bromide salt prepolymer and BASF LR8949, stir at 650 r / min for 30 min, add heptadecanodecyltriethoxysilane modified hollow titanium dioxide particles and stir at 900 r / min for 30 min, then add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF) and stir at 900 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fogging antibacterial coating liquid;

[0080] (3) Apply an antistatic coating liquid to the substrate layer using a micro-gravure coating process, dry at 100℃ for 1 min, and then apply 500 mJ / cm 2 The antistatic base coating is obtained by irradiation with ultraviolet light;

[0081] (4) Apply an anti-fogging and antibacterial coating liquid to the surface of the antistatic primer using a micro-recessed, slit, or doctor blade coating process, dry at 90°C for 2 minutes, and then apply 500 mJ / cm² of coating solution. 2 When exposed to ultraviolet light, an anti-fog, antibacterial, and antistatic coating is obtained.

[0082] Example 6

[0083] An anti-fogging, antibacterial, and antistatic coating comprises, from bottom to top, a substrate layer with a thickness of 120 μm, an antistatic base layer with a thickness of 100 nm, and an anti-fogging and antibacterial coating with a thickness of 3 μm. The substrate layer is made of thermoplastic polyurethane. The antistatic base layer comprises the following raw materials in parts by weight: 12 parts of aliphatic polyurethane acrylate containing -NCO groups (Bayer UA). The antifog and antibacterial coating comprises the following raw materials in parts by weight: VPLS2337), 20 parts pentaerythritol triacrylate (Sartoma SR444), 3 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), 3 parts benzoyl peroxide (Merck), 0.8 parts hexadecyl dimethyl quaternary ammonium nitrate, and 61.5 parts of a mixed solvent, which is obtained by mixing 30.75 parts propylene glycol methyl ether and 30.75 parts isopropanol; the antifog and antibacterial coating comprises the following raw materials in parts by weight: 15 parts allyl alkyl imidazole bromide prepolymer, 5 parts heptadecafluorodecyltriethoxysilane modified hollow titanium dioxide particles, 30 parts BASF LR8949, 5 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), and 45 parts of a mixed solvent, which is obtained by mixing 22.5 parts propylene glycol methyl ether and 22.5 parts isopropanol.

[0084] The allyl alkyl imidazolium bromide prepolymer is prepared through the following steps:

[0085] 1-Allylimidazolium and bromododecane were added to a container in a molar ratio of 1:2, followed by 10 parts by mass of acetonitrile. The mixture was stirred at 60°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allylalkylimidazolium salt monomer. The allylalkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester were mixed in a molar ratio of 1:2:1:5, dissolved in 30 parts by mass of propylene glycol methyl ether, and then 0.5 wt% of pure solid 1-hydroxy-cyclohexyl benzophenone (BASF) was added. The mixture was then irradiated with ultraviolet light to obtain the final product.

[0086] The heptadecanyltriethoxysilane-modified hollow titanium dioxide particles were prepared through the following steps:

[0087] Hollow titanium dioxide was mixed with hydrogen peroxide at a mass ratio of 1:3, sonicated for 30 min, refluxed at 80°C for 4 h, filtered, washed with water, and then vacuum dried at 80°C to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:2 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 20 min. Then, 1 wt% of heptadecafluorodecyltriethoxysilane was added, and the mixture was magnetically stirred at 60°C for 3 h. After filtration, washing with water, and drying at 80°C to constant weight, the final product was obtained.

[0088] The anti-fog, antibacterial, and antistatic coating in this embodiment is prepared through the following steps:

[0089] (1) Mix propylene glycol methyl ether and isopropanol, aliphatic polyurethane acrylate containing -NCO group (Bayer UAVP LS2337) and pentaerythritol triacrylate (Sartoma SR444), stir at 650 r / min for 30 min, add hexadecyl dimethyl quaternary ammonium nitrate, stir at 650 r / min for 5 min, add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), stir at 650 r / min for 5 min, add benzoyl peroxide (Merck), stir at 650 r / min for 5 min, and finally stir at 900 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid.

[0090] (2) Mix propylene glycol methyl ether and isopropanol, allyl alkyl imidazole bromide salt prepolymer and BASF LR8949, stir at 650 r / min for 30 min, add heptadecanodecyltriethoxysilane modified hollow titanium dioxide particles and stir at 900 r / min for 30 min, then add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF) and stir at 900 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fogging antibacterial coating liquid;

[0091] (3) Apply an antistatic coating liquid to the substrate layer using a micro-gravure coating process, dry at 100℃ for 1 min, and then apply 500 mJ / cm 2 The antistatic base coating is obtained by irradiation with ultraviolet light;

[0092] (4) Apply an anti-fogging and antibacterial coating liquid to the surface of the antistatic primer using a micro-recessed, slit, or doctor blade coating process, dry at 90°C for 2 minutes, and then apply 500 mJ / cm² of coating solution. 2 When exposed to ultraviolet light, an anti-fog, antibacterial, and antistatic coating is obtained.

[0093] Example 7

[0094] An anti-fogging, antibacterial, and antistatic coating comprises, from bottom to top, a substrate layer with a thickness of 120 μm, an antistatic base layer with a thickness of 120 nm, and an anti-fogging and antibacterial coating with a thickness of 3 μm. The substrate layer is made of thermoplastic polyurethane. The antistatic base layer comprises the following raw materials in parts by weight: 12 parts of aliphatic polyurethane acrylate containing -NCO groups (Bayer UA). The antifog and antibacterial coating comprises the following raw materials in parts by weight: VPLS2337), 20 parts pentaerythritol triacrylate (Sartoma SR444), 3 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), 3 parts benzoyl peroxide (Merck), 0.5 parts hexadecyl dimethyl quaternary ammonium nitrate, and 61.5 parts of a mixed solvent, which is obtained by mixing 30.75 parts propylene glycol methyl ether and 30.75 parts isopropanol; the antifog and antibacterial coating comprises the following raw materials in parts by weight: 15 parts allyl alkyl imidazole bromide prepolymer, 5 parts heptadecafluorodecyltriethoxysilane modified hollow titanium dioxide particles, 30 parts BASF LR8949, 5 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), and 45 parts of a mixed solvent, which is obtained by mixing 22.5 parts propylene glycol methyl ether and 22.5 parts isopropanol.

[0095] The allyl alkyl imidazolium bromide prepolymer is prepared through the following steps:

[0096] 1-Allylimidazolium and bromododecane were added to a container in a molar ratio of 1:2, followed by 10 parts by mass of acetonitrile. The mixture was stirred at 60°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allylalkylimidazolium salt monomer. The allylalkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester were mixed in a molar ratio of 1:2:1:5, dissolved in 30 parts by mass of propylene glycol methyl ether, and then 0.5 wt% of pure solid 1-hydroxy-cyclohexyl benzophenone (BASF) was added. The mixture was then irradiated with ultraviolet light to obtain the final product.

[0097] The heptadecanyltriethoxysilane-modified hollow titanium dioxide particles were prepared through the following steps:

[0098] Hollow titanium dioxide was mixed with hydrogen peroxide at a mass ratio of 1:3, sonicated for 30 min, refluxed at 80°C for 4 h, filtered, washed with water, and then vacuum dried at 80°C to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:2 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 20 min. Then, 1 wt% of heptadecafluorodecyltriethoxysilane was added, and the mixture was magnetically stirred at 60°C for 3 h. After filtration, washing with water, and drying at 80°C to constant weight, the final product was obtained.

[0099] The anti-fog, antibacterial, and antistatic coating in this embodiment is prepared through the following steps:

[0100] (1) Mix propylene glycol methyl ether and isopropanol, aliphatic polyurethane acrylate containing -NCO group (Bayer UAVP LS2337) and pentaerythritol triacrylate (Sartoma SR444), stir at 650 r / min for 30 min, add hexadecyl dimethyl quaternary ammonium nitrate, stir at 650 r / min for 5 min, add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), stir at 650 r / min for 5 min, add benzoyl peroxide (Merck), stir at 650 r / min for 5 min, and finally stir at 900 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid.

[0101] (2) Mix propylene glycol methyl ether and isopropanol, allyl alkyl imidazole bromide salt prepolymer and BASF LR8949, stir at 650 r / min for 30 min, add heptadecanodecyltriethoxysilane modified hollow titanium dioxide particles and stir at 900 r / min for 30 min, then add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF) and stir at 900 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fogging antibacterial coating liquid;

[0102] (3) Apply an antistatic coating liquid to the substrate layer using a micro-gravure coating process, dry at 100℃ for 1 min, and then apply 500 mJ / cm 2 The antistatic base coating is obtained by irradiation with ultraviolet light;

[0103] (4) Apply an anti-fogging and antibacterial coating liquid to the surface of the antistatic primer using a micro-recessed, slit, or doctor blade coating process, dry at 90°C for 2 minutes, and then apply 500 mJ / cm² of coating solution. 2 When exposed to ultraviolet light, an anti-fog, antibacterial, and antistatic coating is obtained.

[0104] Example 8

[0105] An anti-fogging, antibacterial, and antistatic coating comprises, from bottom to top, a substrate layer with a thickness of 120 μm, an antistatic base layer with a thickness of 100 nm, and an anti-fogging and antibacterial coating with a thickness of 3 μm. The substrate layer is made of thermoplastic polyurethane. The antistatic base layer comprises the following raw materials in parts by weight: 12 parts of aliphatic polyurethane acrylate containing -NCO groups (Bayer UA). The antifog and antibacterial coating comprises the following raw materials in parts by weight: VPLS2337), 20 parts pentaerythritol triacrylate (Sartoma SR444), 3 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), 3 parts benzoyl peroxide (Merck), 0.5 parts hexadecyl dimethyl quaternary ammonium nitrate, and 61.5 parts of a mixed solvent, which is obtained by mixing 30.75 parts propylene glycol methyl ether and 30.75 parts isopropanol; the antifog and antibacterial coating comprises the following raw materials in parts by weight: 15 parts allyl alkyl imidazole bromide prepolymer, 5 parts heptadecafluorodecyltriethoxysilane modified hollow titanium dioxide particles, 30 parts BASF LR8949, 5 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), and 45 parts of a mixed solvent, which is obtained by mixing 22.5 parts propylene glycol methyl ether and 22.5 parts isopropanol.

[0106] The allyl alkyl imidazolium bromide prepolymer is prepared through the following steps:

[0107] 1-Allylimidazolium and n-octane bromide were added to a container in a molar ratio of 1:2, followed by 10 parts by mass of acetonitrile. The mixture was stirred at 60°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allyl alkylimidazolium salt monomer. The allyl alkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester were mixed in a molar ratio of 1:2:1:5, dissolved in 30 parts by mass of propylene glycol methyl ether, and then 0.5 wt% of pure solid 1-hydroxy-cyclohexyl benzophenone (BASF) was added. The mixture was then irradiated with ultraviolet light to obtain the final product.

[0108] The heptadecanyltriethoxysilane-modified hollow titanium dioxide particles were prepared through the following steps:

[0109] Hollow titanium dioxide was mixed with hydrogen peroxide at a mass ratio of 1:3, sonicated for 30 min, refluxed at 80°C for 4 h, filtered, washed with water, and then vacuum dried at 80°C to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:2 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 20 min. Then, 1 wt% of heptadecafluorodecyltriethoxysilane was added, and the mixture was magnetically stirred at 60°C for 3 h. After filtration, washing with water, and drying at 80°C to constant weight, the final product was obtained.

[0110] The anti-fog, antibacterial, and antistatic coating in this embodiment is prepared through the following steps:

[0111] (1) Mix propylene glycol methyl ether and isopropanol, aliphatic polyurethane acrylate containing -NCO group (Bayer UAVP LS2337) and pentaerythritol triacrylate (Sartoma SR444), stir at 650 r / min for 30 min, add hexadecyl dimethyl quaternary ammonium nitrate, stir at 650 r / min for 5 min, add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), stir at 650 r / min for 5 min, add benzoyl peroxide (Merck), stir at 650 r / min for 5 min, and finally stir at 900 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid.

[0112] (2) Mix propylene glycol methyl ether and isopropanol, allyl alkyl imidazole bromide salt prepolymer and BASF LR8949, stir at 650 r / min for 30 min, add heptadecanodecyltriethoxysilane modified hollow titanium dioxide particles and stir at 900 r / min for 30 min, then add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF) and stir at 900 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fogging antibacterial coating liquid;

[0113] (3) Apply an antistatic coating liquid to the substrate layer using a micro-gravure coating process, dry at 100℃ for 1 min, and then apply 500 mJ / cm 2 The antistatic base coating is obtained by irradiation with ultraviolet light;

[0114] (4) Apply an anti-fogging and antibacterial coating liquid to the surface of the antistatic primer using a micro-recessed, slit, or doctor blade coating process, dry at 90°C for 2 minutes, and then apply 500 mJ / cm² of coating solution. 2 When exposed to ultraviolet light, an anti-fog, antibacterial, and antistatic coating is obtained.

[0115] Example 9

[0116] An anti-fogging, antibacterial, and antistatic coating comprises, from bottom to top, a substrate layer with a thickness of 120 μm, an antistatic base layer with a thickness of 100 nm, and an anti-fogging and antibacterial coating with a thickness of 3 μm. The substrate layer is made of thermoplastic polyurethane. The antistatic base layer comprises the following raw materials in parts by weight: 12 parts of aliphatic polyurethane acrylate containing -NCO groups (Bayer UA). The antifog and antibacterial coating comprises the following raw materials in parts by weight: VPLS2337), 20 parts pentaerythritol triacrylate (Sartoma SR444), 3 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), 3 parts benzoyl peroxide (Merck), 0.5 parts hexadecyl dimethyl quaternary ammonium nitrate, and 61.5 parts of a mixed solvent, which is obtained by mixing 30.75 parts propylene glycol methyl ether and 30.75 parts isopropanol; the antifog and antibacterial coating comprises the following raw materials in parts by weight: 15 parts allyl alkyl imidazole bromide prepolymer, 5 parts heptadecafluorodecyltriethoxysilane modified hollow titanium dioxide particles, 30 parts BASF LR8949, 5 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), and 45 parts of a mixed solvent, which is obtained by mixing 22.5 parts propylene glycol methyl ether and 22.5 parts isopropanol.

[0117] The allyl alkyl imidazolium bromide prepolymer is prepared through the following steps:

[0118] 1-Allylimidazolium and bromododecane were added to a container in a molar ratio of 1:2, followed by 10 parts by mass of acetonitrile. The mixture was stirred at 60°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allylalkylimidazolium salt monomer. The allylalkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester were mixed in a molar ratio of 1:1:2:5, dissolved in 30 parts by mass of propylene glycol methyl ether, and then 0.5 wt% of pure solid 1-hydroxy-cyclohexyl benzophenone (BASF) was added. The mixture was then irradiated with ultraviolet light to obtain the final product.

[0119] The heptadecanyltriethoxysilane-modified hollow titanium dioxide particles were prepared through the following steps:

[0120] Hollow titanium dioxide was mixed with hydrogen peroxide at a mass ratio of 1:3, sonicated for 30 min, refluxed at 80°C for 4 h, filtered, washed with water, and then vacuum dried at 80°C to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:2 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 20 min. Then, 1 wt% of heptadecafluorodecyltriethoxysilane was added, and the mixture was magnetically stirred at 60°C for 3 h. After filtration, washing with water, and drying at 80°C to constant weight, the final product was obtained.

[0121] The anti-fog, antibacterial, and antistatic coating in this embodiment is prepared through the following steps:

[0122] (1) Mix propylene glycol methyl ether and isopropanol, aliphatic polyurethane acrylate containing -NCO group (Bayer UAVP LS2337) and pentaerythritol triacrylate (Sartoma SR444), stir at 650 r / min for 30 min, add hexadecyl dimethyl quaternary ammonium nitrate, stir at 650 r / min for 5 min, add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), stir at 650 r / min for 5 min, add benzoyl peroxide (Merck), stir at 650 r / min for 5 min, and finally stir at 900 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid.

[0123] (2) Mix propylene glycol methyl ether and isopropanol, allyl alkyl imidazole bromide salt prepolymer and BASF LR8949, stir at 650 r / min for 30 min, add heptadecanodecyltriethoxysilane modified hollow titanium dioxide particles and stir at 900 r / min for 30 min, then add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF) and stir at 900 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fogging antibacterial coating liquid;

[0124] (3) Apply an antistatic coating liquid to the substrate layer using a micro-gravure coating process, dry at 100℃ for 1 min, and then apply 500 mJ / cm 2 The antistatic base coating is obtained by irradiation with ultraviolet light;

[0125] (4) Apply an anti-fogging and antibacterial coating liquid to the surface of the antistatic primer using a micro-recessed, slit, or doctor blade coating process, dry at 90°C for 2 minutes, and then apply 500 mJ / cm² of coating solution. 2 When exposed to ultraviolet light, an anti-fog, antibacterial, and antistatic coating is obtained.

[0126] Example 10

[0127] An anti-fogging, antibacterial, and antistatic coating comprises, from bottom to top, a substrate layer with a thickness of 120 μm, an antistatic base layer with a thickness of 100 nm, and an anti-fogging and antibacterial coating with a thickness of 3 μm. The substrate layer is made of thermoplastic polyurethane. The antistatic base layer comprises the following raw materials in parts by weight: 12 parts of aliphatic polyurethane acrylate containing -NCO groups (Bayer UA). The antifog and antibacterial coating comprises the following raw materials in parts by weight: VPLS2337), 20 parts pentaerythritol triacrylate (Sartoma SR444), 3 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), 3 parts benzoyl peroxide (Merck), 0.5 parts hexadecyl dimethyl quaternary ammonium nitrate, and 61.5 parts of a mixed solvent, which is obtained by mixing 30.75 parts propylene glycol methyl ether and 30.75 parts isopropanol; the antifog and antibacterial coating comprises the following raw materials in parts by weight: 15 parts allyl alkyl imidazole bromide prepolymer, 5 parts heptadecafluorodecyltriethoxysilane modified hollow titanium dioxide particles, 30 parts BASF LR8949, 5 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), and 45 parts of a mixed solvent, which is obtained by mixing 22.5 parts propylene glycol methyl ether and 22.5 parts isopropanol.

[0128] The allyl alkyl imidazolium bromide prepolymer is prepared through the following steps:

[0129] 1-Allylimidazolium and bromododecane were added to a container in a molar ratio of 1:2, followed by 10 parts by mass of acetonitrile. The mixture was stirred at 60°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allylalkylimidazolium salt monomer. The allylalkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester were mixed in a molar ratio of 1:2:1:5, dissolved in 30 parts by mass of propylene glycol methyl ether, and then 1 wt% of pure solid 1-hydroxy-cyclohexyl benzophenone (BASF) was added. The mixture was then irradiated with ultraviolet light to obtain the final product.

[0130] The heptadecanyltriethoxysilane-modified hollow titanium dioxide particles were prepared through the following steps:

[0131] Hollow titanium dioxide was mixed with hydrogen peroxide at a mass ratio of 1:3, sonicated for 30 min, refluxed at 80°C for 4 h, filtered, washed with water, and then vacuum dried at 80°C to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:2 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 20 min. Then, 1 wt% of heptadecafluorodecyltriethoxysilane was added, and the mixture was magnetically stirred at 60°C for 3 h. After filtration, washing with water, and drying at 80°C to constant weight, the final product was obtained.

[0132] The anti-fog, antibacterial, and antistatic coating in this embodiment is prepared through the following steps:

[0133] (1) Mix propylene glycol methyl ether and isopropanol, aliphatic polyurethane acrylate containing -NCO group (Bayer UAVP LS2337) and pentaerythritol triacrylate (Sartoma SR444), stir at 650 r / min for 30 min, add hexadecyl dimethyl quaternary ammonium nitrate, stir at 650 r / min for 5 min, add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), stir at 650 r / min for 5 min, add benzoyl peroxide (Merck), stir at 650 r / min for 5 min, and finally stir at 900 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid.

[0134] (2) Mix propylene glycol methyl ether and isopropanol, allyl alkyl imidazole bromide salt prepolymer and BASF LR8949, stir at 650 r / min for 30 min, add heptadecanodecyltriethoxysilane modified hollow titanium dioxide particles and stir at 900 r / min for 30 min, then add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF) and stir at 900 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fogging antibacterial coating liquid;

[0135] (3) Apply an antistatic coating liquid to the substrate layer using a micro-gravure coating process, dry at 100℃ for 1 min, and then apply 500 mJ / cm 2 The antistatic base coating is obtained by irradiation with ultraviolet light;

[0136] (4) Apply an anti-fogging and antibacterial coating liquid to the surface of the antistatic primer using a micro-recessed, slit, or doctor blade coating process, dry at 90°C for 2 minutes, and then apply 500 mJ / cm² of coating solution. 2 When exposed to ultraviolet light, an anti-fog, antibacterial, and antistatic coating is obtained.

[0137] Example 11

[0138] An anti-fogging, antibacterial, and antistatic coating comprises, from bottom to top, a substrate layer with a thickness of 120 μm, an antistatic base layer with a thickness of 100 nm, and an anti-fogging and antibacterial coating with a thickness of 3 μm. The substrate layer is made of thermoplastic polyurethane. The antistatic base layer comprises the following raw materials in parts by weight: 12 parts of aliphatic polyurethane acrylate containing -NCO groups (Bayer UA). The antifog and antibacterial coating comprises the following raw materials in parts by weight: VPLS2337), 20 parts pentaerythritol triacrylate (Sartoma SR444), 3 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), 3 parts benzoyl peroxide (Merck), 0.5 parts hexadecyl dimethyl quaternary ammonium nitrate, and 61.5 parts a mixed solvent, which is obtained by mixing 30.75 parts propylene glycol methyl ether and 30.75 parts isopropanol; the antifog and antibacterial coating comprises the following raw materials in parts by weight: 15 parts allyl alkyl imidazole bromide prepolymer, 5 parts tridecafluorooctyltriethoxysilane modified hollow titanium dioxide particles, 30 parts BASF LR8949, 5 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), and 45 parts a mixed solvent, which is obtained by mixing 22.5 parts propylene glycol methyl ether and 22.5 parts isopropanol.

[0139] The allyl alkyl imidazolium bromide prepolymer is prepared through the following steps:

[0140] 1-Allylimidazolium and bromododecane were added to a container in a molar ratio of 1:2, followed by 10 parts by mass of acetonitrile. The mixture was stirred at 60°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allylalkylimidazolium salt monomer. The allylalkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester were mixed in a molar ratio of 1:2:1:5, dissolved in 30 parts by mass of propylene glycol methyl ether, and then 0.5 wt% of pure solid 1-hydroxy-cyclohexyl benzophenone (BASF) was added. The mixture was then irradiated with ultraviolet light to obtain the final product.

[0141] The tridecafluorooctyltriethoxysilane-modified hollow titanium dioxide particles were prepared through the following steps:

[0142] Hollow titanium dioxide was mixed with hydrogen peroxide at a mass ratio of 1:3, sonicated for 30 min, refluxed at 80°C for 4 h, filtered, washed with water, and then vacuum dried at 80°C to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:2 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 20 min. Then 1 wt% of tridecafluorooctyltriethoxysilane was added, and the mixture was magnetically stirred at 60°C for 3 h. After filtration, washing with water, and drying at 80°C to constant weight, the final product was obtained.

[0143] The anti-fog, antibacterial, and antistatic coating in this embodiment is prepared through the following steps:

[0144] (1) Mix propylene glycol methyl ether and isopropanol, aliphatic polyurethane acrylate containing -NCO group (Bayer UAVP LS2337) and pentaerythritol triacrylate (Sartoma SR444), stir at 650 r / min for 30 min, add hexadecyl dimethyl quaternary ammonium nitrate, stir at 650 r / min for 5 min, add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), stir at 650 r / min for 5 min, add benzoyl peroxide (Merck), stir at 650 r / min for 5 min, and finally stir at 900 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid.

[0145] (2) Mix propylene glycol methyl ether and isopropanol, allyl alkyl imidazole bromide prepolymer and BASF LR8949, stir at 650 r / min for 30 min, add tridecafluorooctyltriethoxysilane modified hollow titanium dioxide particles and stir at 900 r / min for 30 min, then add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF) and stir at 900 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fogging antibacterial coating liquid;

[0146] (3) Apply an antistatic coating liquid to the substrate layer using a micro-gravure coating process, dry at 100℃ for 1 min, and then apply 500 mJ / cm 2 The antistatic base coating is obtained by irradiation with ultraviolet light;

[0147] (4) Apply an anti-fogging and antibacterial coating liquid to the surface of the antistatic primer using a micro-recessed, slit, or doctor blade coating process, dry at 90°C for 2 minutes, and then apply 500 mJ / cm² of coating solution. 2 When exposed to ultraviolet light, an anti-fog, antibacterial, and antistatic coating is obtained.

[0148] Example 12

[0149] An anti-fogging, antibacterial, and antistatic coating comprises, from bottom to top, a substrate layer with a thickness of 120 μm, an antistatic base layer with a thickness of 100 nm, and an anti-fogging and antibacterial coating with a thickness of 3 μm. The substrate layer is made of thermoplastic polyurethane. The antistatic base layer comprises the following raw materials in parts by weight: 12 parts of aliphatic polyurethane acrylate containing -NCO groups (Bayer UA). The antifog and antibacterial coating comprises the following raw materials in parts by weight: VPLS2337), 20 parts pentaerythritol triacrylate (Sartoma SR444), 3 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), 3 parts benzoyl peroxide (Merck), 0.5 parts hexadecyl dimethyl quaternary ammonium nitrate, and 61.5 parts of a mixed solvent, which is obtained by mixing 30.75 parts propylene glycol methyl ether and 30.75 parts isopropanol; the antifog and antibacterial coating comprises the following raw materials in parts by weight: 15 parts allyl alkyl imidazole bromide prepolymer, 8 parts heptadecafluorodecyltriethoxysilane modified hollow titanium dioxide particles, 30 parts BASF LR8949, 5 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), and 45 parts of a mixed solvent, which is obtained by mixing 22.5 parts propylene glycol methyl ether and 22.5 parts isopropanol.

[0150] The allyl alkyl imidazolium bromide prepolymer is prepared through the following steps:

[0151] 1-Allylimidazolium and bromododecane were added to a container in a molar ratio of 1:2, followed by 10 parts by mass of acetonitrile. The mixture was stirred at 60°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allylalkylimidazolium salt monomer. The allylalkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester were mixed in a molar ratio of 1:2:1:5, dissolved in 30 parts by mass of propylene glycol methyl ether, and then 0.5 wt% of pure solid 1-hydroxy-cyclohexyl benzophenone (BASF) was added. The mixture was then irradiated with ultraviolet light to obtain the final product.

[0152] The heptadecanyltriethoxysilane-modified hollow titanium dioxide particles were prepared through the following steps:

[0153] Hollow titanium dioxide was mixed with hydrogen peroxide at a mass ratio of 1:3, sonicated for 30 min, refluxed at 80°C for 4 h, filtered, washed with water, and then vacuum dried at 80°C to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:2 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 20 min. Then, 1 wt% of heptadecafluorodecyltriethoxysilane was added, and the mixture was magnetically stirred at 60°C for 3 h. After filtration, washing with water, and drying at 80°C to constant weight, the final product was obtained.

[0154] The anti-fog, antibacterial, and antistatic coating in this embodiment is prepared through the following steps:

[0155] (1) Mix propylene glycol methyl ether and isopropanol, aliphatic polyurethane acrylate containing -NCO group (Bayer UAVP LS2337) and pentaerythritol triacrylate (Sartoma SR444), stir at 650 r / min for 30 min, add hexadecyl dimethyl quaternary ammonium nitrate, stir at 650 r / min for 5 min, add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), stir at 650 r / min for 5 min, add benzoyl peroxide (Merck), stir at 650 r / min for 5 min, and finally stir at 900 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid.

[0156] (2) Mix propylene glycol methyl ether and isopropanol, allyl alkyl imidazole bromide salt prepolymer and BASF LR8949, stir at 650 r / min for 30 min, add heptadecanodecyltriethoxysilane modified hollow titanium dioxide particles and stir at 900 r / min for 30 min, then add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF) and stir at 900 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fogging antibacterial coating liquid;

[0157] (3) Apply an antistatic coating liquid to the substrate layer using a micro-gravure coating process, dry at 100℃ for 1 min, and then apply 500 mJ / cm 2 The antistatic base coating is obtained by irradiation with ultraviolet light;

[0158] (4) Apply an anti-fogging and antibacterial coating liquid to the surface of the antistatic primer using a micro-recessed, slit, or doctor blade coating process, dry at 90°C for 2 minutes, and then apply 500 mJ / cm² of coating solution. 2 When exposed to ultraviolet light, an anti-fog, antibacterial, and antistatic coating is obtained.

[0159] Example 13

[0160] An anti-fogging, antibacterial, and antistatic coating comprises, from bottom to top, a substrate layer with a thickness of 120 μm, an antistatic base layer with a thickness of 100 nm, and an anti-fogging and antibacterial coating with a thickness of 3 μm. The substrate layer is made of thermoplastic polyurethane. The antistatic base layer comprises the following raw materials in parts by weight: 12 parts of aliphatic polyurethane acrylate containing -NCO groups (Bayer UA). The anti-fog and antibacterial coating comprises the following raw materials in parts by weight: VPLS2337), 20 parts pentaerythritol triacrylate (Sartoma SR444), 3 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), 3 parts benzoyl peroxide (Merck), 0.5 parts hexadecyl dimethyl quaternary ammonium nitrate, and 61.5 parts a mixed solvent, which is obtained by mixing 30.75 parts propylene glycol methyl ether and 30.75 parts isopropanol; the anti-fog and antibacterial coating comprises the following raw materials in parts by weight: 15 parts allyl alkyl imidazole bromide prepolymer, 5 parts heptadecafluorodecyltriethoxysilane modified hollow titanium dioxide particles, 30 parts Changxing DR-W450, 5 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), and 45 parts a mixed solvent, which is obtained by mixing 22.5 parts propylene glycol methyl ether and 22.5 parts isopropanol.

[0161] The allyl alkyl imidazolium bromide prepolymer is prepared through the following steps:

[0162] 1-Allylimidazolium and bromododecane were added to a container in a molar ratio of 1:2, followed by 10 parts by mass of acetonitrile. The mixture was stirred at 60°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allylalkylimidazolium salt monomer. The allylalkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester were mixed in a molar ratio of 1:2:1:5, dissolved in 30 parts by mass of propylene glycol methyl ether, and then 0.5 wt% of pure solid 1-hydroxy-cyclohexyl benzophenone (BASF) was added. The mixture was then irradiated with ultraviolet light to obtain the final product.

[0163] The heptadecanyltriethoxysilane-modified hollow titanium dioxide particles were prepared through the following steps:

[0164] Hollow titanium dioxide was mixed with hydrogen peroxide at a mass ratio of 1:3, sonicated for 30 min, refluxed at 80°C for 4 h, filtered, washed with water, and then vacuum dried at 80°C to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:2 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 20 min. Then, 1 wt% of heptadecafluorodecyltriethoxysilane was added, and the mixture was magnetically stirred at 60°C for 3 h. After filtration, washing with water, and drying at 80°C to constant weight, the final product was obtained.

[0165] The anti-fog, antibacterial, and antistatic coating in this embodiment is prepared through the following steps:

[0166] (1) Mix propylene glycol methyl ether and isopropanol, aliphatic polyurethane acrylate containing -NCO group (Bayer UAVP LS2337) and pentaerythritol triacrylate (Sartoma SR444), stir at 650 r / min for 30 min, add hexadecyl dimethyl quaternary ammonium nitrate, stir at 650 r / min for 5 min, add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), stir at 650 r / min for 5 min, add benzoyl peroxide (Merck), stir at 650 r / min for 5 min, and finally stir at 900 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid.

[0167] (2) Mix propylene glycol methyl ether and isopropanol, allyl alkyl imidazole bromide salt prepolymer and Changxing DR-W450, stir at 650 r / min for 30 min, add heptadecanodecyltriethoxysilane modified hollow titanium dioxide particles and stir at 900 r / min for 30 min, then add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF) and stir at 900 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fogging antibacterial coating liquid;

[0168] (3) Apply an antistatic coating liquid to the substrate layer using a micro-gravure coating process, dry at 100℃ for 1 min, and then apply 500 mJ / cm 2 The antistatic base coating is obtained by irradiation with ultraviolet light;

[0169] (4) Apply an anti-fogging and antibacterial coating liquid to the surface of the antistatic primer using a micro-recessed, slit, or doctor blade coating process, dry at 90°C for 2 minutes, and then apply 500 mJ / cm² of coating solution. 2 When exposed to ultraviolet light, an anti-fog, antibacterial, and antistatic coating is obtained.

[0170] Example 14

[0171] An anti-fogging, antibacterial, and antistatic coating comprises, from bottom to top, a substrate layer with a thickness of 120 μm, an antistatic base layer with a thickness of 100 nm, and an anti-fogging and antibacterial coating with a thickness of 3 μm. The substrate layer is made of thermoplastic polyurethane. The antistatic base layer comprises the following raw materials in parts by weight: 12 parts of aliphatic polyurethane acrylate containing -NCO groups (Bayer UA). The antifog and antibacterial coating comprises the following raw materials in parts by weight: VPLS2337), 20 parts pentaerythritol triacrylate (Sartoma SR444), 3 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), 3 parts benzoyl peroxide (Merck), 0.5 parts hexadecyl dimethyl quaternary ammonium nitrate, and 61.5 parts of a mixed solvent, which is obtained by mixing 30.75 parts propylene glycol methyl ether and 30.75 parts isopropanol; the antifog and antibacterial coating comprises the following raw materials in parts by weight: 15 parts allyl alkyl imidazole bromide prepolymer, 5 parts heptadecafluorodecyltriethoxysilane modified hollow titanium dioxide particles, 30 parts BASF LR8949, 3 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), and 45 parts of a mixed solvent, which is obtained by mixing 22.5 parts propylene glycol methyl ether and 22.5 parts isopropanol.

[0172] The allyl alkyl imidazolium bromide prepolymer is prepared through the following steps:

[0173] 1-Allylimidazolium and bromododecane were added to a container in a molar ratio of 1:2, followed by 10 parts by mass of acetonitrile. The mixture was stirred at 60°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allylalkylimidazolium salt monomer. The allylalkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester were mixed in a molar ratio of 1:2:1:5, dissolved in 30 parts by mass of propylene glycol methyl ether, and then 0.5 wt% of pure solid 1-hydroxy-cyclohexyl benzophenone (BASF) was added. The mixture was then irradiated with ultraviolet light to obtain the final product.

[0174] The heptadecanyltriethoxysilane-modified hollow titanium dioxide particles were prepared through the following steps:

[0175] Hollow titanium dioxide was mixed with hydrogen peroxide at a mass ratio of 1:3, sonicated for 30 min, refluxed at 80°C for 4 h, filtered, washed with water, and then vacuum dried at 80°C to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:2 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 20 min. Then, 1 wt% of heptadecafluorodecyltriethoxysilane was added, and the mixture was magnetically stirred at 60°C for 3 h. After filtration, washing with water, and drying at 80°C to constant weight, the final product was obtained.

[0176] The anti-fog, antibacterial, and antistatic coating in this embodiment is prepared through the following steps:

[0177] (1) Mix propylene glycol methyl ether and isopropanol, aliphatic polyurethane acrylate containing -NCO group (Bayer UAVP LS2337) and pentaerythritol triacrylate (Sartoma SR444), stir at 650 r / min for 30 min, add hexadecyl dimethyl quaternary ammonium nitrate, stir at 650 r / min for 5 min, add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), stir at 650 r / min for 5 min, add benzoyl peroxide (Merck), stir at 650 r / min for 5 min, and finally stir at 900 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid.

[0178] (2) Mix propylene glycol methyl ether and isopropanol, allyl alkyl imidazole bromide salt prepolymer and BASF LR8949, stir at 650 r / min for 30 min, add heptadecanodecyltriethoxysilane modified hollow titanium dioxide particles and stir at 900 r / min for 30 min, then add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF) and stir at 900 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fogging antibacterial coating liquid;

[0179] (3) Apply an antistatic coating liquid to the substrate layer using a micro-gravure coating process, dry at 100℃ for 1 min, and then apply 500 mJ / cm 2 The antistatic base coating is obtained by irradiation with ultraviolet light;

[0180] (4) Apply an anti-fogging and antibacterial coating liquid to the surface of the antistatic primer using a micro-recessed, slit, or doctor blade coating process, dry at 90°C for 2 minutes, and then apply 500 mJ / cm² of coating solution. 2 When exposed to ultraviolet light, an anti-fog, antibacterial, and antistatic coating is obtained.

[0181] Example 15

[0182] An anti-fogging, antibacterial, and antistatic coating comprises, from bottom to top, a substrate layer with a thickness of 120 μm, an antistatic base layer with a thickness of 100 nm, and an anti-fogging and antibacterial coating with a thickness of 5 μm. The substrate layer is made of thermoplastic polyurethane. The antistatic base layer comprises the following raw materials in parts by weight: 12 parts of aliphatic polyurethane acrylate containing -NCO groups (Bayer UA). The antifog and antibacterial coating comprises the following raw materials in parts by weight: VPLS2337), 20 parts pentaerythritol triacrylate (Sartoma SR444), 3 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), 3 parts benzoyl peroxide (Merck), 0.5 parts hexadecyl dimethyl quaternary ammonium nitrate, and 61.5 parts of a mixed solvent, which is obtained by mixing 30.75 parts propylene glycol methyl ether and 30.75 parts isopropanol; the antifog and antibacterial coating comprises the following raw materials in parts by weight: 15 parts allyl alkyl imidazole bromide prepolymer, 5 parts heptadecafluorodecyltriethoxysilane modified hollow titanium dioxide particles, 30 parts BASF LR8949, 5 parts 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), and 45 parts of a mixed solvent, which is obtained by mixing 22.5 parts propylene glycol methyl ether and 22.5 parts isopropanol.

[0183] The allyl alkyl imidazolium bromide prepolymer is prepared through the following steps:

[0184] 1-Allylimidazolium and bromododecane were added to a container in a molar ratio of 1:2, followed by 10 parts by mass of acetonitrile. The mixture was stirred at 60°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allylalkylimidazolium salt monomer. The allylalkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester were mixed in a molar ratio of 1:2:1:5, dissolved in 30 parts by mass of propylene glycol methyl ether, and then 0.5 wt% of pure solid 1-hydroxy-cyclohexyl benzophenone (BASF) was added. The mixture was then irradiated with ultraviolet light to obtain the final product.

[0185] The heptadecanyltriethoxysilane-modified hollow titanium dioxide particles were prepared through the following steps:

[0186] Hollow titanium dioxide was mixed with hydrogen peroxide at a mass ratio of 1:3, sonicated for 30 min, refluxed at 80°C for 4 h, filtered, washed with water, and then vacuum dried at 80°C to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:2 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 20 min. Then, 1 wt% of heptadecafluorodecyltriethoxysilane was added, and the mixture was magnetically stirred at 60°C for 3 h. After filtration, washing with water, and drying at 80°C to constant weight, the final product was obtained.

[0187] The anti-fog, antibacterial, and antistatic coating in this embodiment is prepared through the following steps:

[0188] (1) Mix propylene glycol methyl ether and isopropanol, aliphatic polyurethane acrylate containing -NCO group (Bayer UAVP LS2337) and pentaerythritol triacrylate (Sartoma SR444), stir at 650 r / min for 30 min, add hexadecyl dimethyl quaternary ammonium nitrate, stir at 650 r / min for 5 min, add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF), stir at 650 r / min for 5 min, add benzoyl peroxide (Merck), stir at 650 r / min for 5 min, and finally stir at 900 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid.

[0189] (2) Mix propylene glycol methyl ether and isopropanol, allyl alkyl imidazole bromide salt prepolymer and BASF LR8949, stir at 650 r / min for 30 min, add heptadecanodecyltriethoxysilane modified hollow titanium dioxide particles and stir at 900 r / min for 30 min, then add 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF) and stir at 900 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fogging antibacterial coating liquid;

[0190] (3) Apply an antistatic coating liquid to the substrate layer using a micro-gravure coating process, dry at 100℃ for 1 min, and then apply 500 mJ / cm 2 The antistatic base coating is obtained by irradiation with ultraviolet light;

[0191] (4) Apply an anti-fogging and antibacterial coating liquid to the surface of the antistatic primer using a micro-recessed, slit, or doctor blade coating process, dry at 90°C for 2 minutes, and then apply 500 mJ / cm² of coating solution. 2 When exposed to ultraviolet light, an anti-fog, antibacterial, and antistatic coating is obtained.

[0192] Comparative Example 1

[0193] An anti-fog, antibacterial, and antistatic coating, compared to Example 1, does not contain an antistatic primer.

[0194] Comparative Example 2

[0195] A fog-proof, antibacterial, and antistatic coating, compared to Example 1, in which benzoyl peroxide was not added during the preparation of the antistatic base coating.

[0196] Comparative Example 3

[0197] An anti-fog, antibacterial, and antistatic coating, compared with Example 1, wherein the amount of 2-hydroxy-2-methyl-1-phenyl-1-propanone added is 10 parts by weight in both the preparation of the antistatic primer and the anti-fog and antibacterial coating.

[0198] Comparative Example 4

[0199] An anti-fog, antibacterial, and antistatic coating, compared to Example 1, does not contain hexadecyl dimethyl quaternary ammonium nitrate during the preparation of the antistatic base coating.

[0200] Comparative Example 5

[0201] An anti-fog, antibacterial, and antistatic coating, compared with Example 1, wherein the amount of hexadecyl dimethyl quaternary ammonium nitrate added during the preparation of the antistatic base coating is 1 part by mass.

[0202] Comparative Example 6

[0203] An anti-fog, antibacterial, and antistatic coating is provided, with the antistatic base coating having a thickness of 150 nm compared to Example 1.

[0204] Comparative Example 7

[0205] An anti-fogging, antibacterial, and antistatic coating, compared with Example 1, uses bromoalkane instead of hexadecane in the preparation of the allyl alkyl imidazole bromide prepolymer.

[0206] Comparative Example 8

[0207] An anti-fogging, antibacterial, and antistatic coating, compared with Example 1, does not add allyl alkyl imidazolium salt monomer during the preparation of allyl alkyl imidazolium bromide prepolymer, and the molar ratio of 1,3-diallyl imidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester is 1:2:5.

[0208] Comparative Example 9

[0209] An anti-fogging, antibacterial, and antistatic coating, compared to Example 1, has a 1-hydroxy-cyclohexylbenzophenone content of 3 wt% in pure solids during the preparation of the allyl alkyl imidazolium bromide prepolymer.

[0210] Comparative Example 10

[0211] An anti-fog, antibacterial, and antistatic coating, compared to Example 1, in which 2-hydroxy-2-methyl-1-phenyl-1-propanone was not added during the preparation of the anti-fog and antibacterial coating.

[0212] Comparative Example 11

[0213] An anti-fog, antibacterial, and antistatic coating, compared with Example 1, replaces the heptadecanodecyltriethoxysilane-modified hollow titanium dioxide particles with unmodified hollow titanium dioxide particles during the preparation of the anti-fog and antibacterial coating.

[0214] Comparative Example 12

[0215] An anti-fog, antibacterial, and antistatic coating is provided. Compared with Example 1, the amount of heptadecafluorodecyltriethoxysilane-modified hollow titanium dioxide particles added during the preparation of the anti-fog and antibacterial coating is 20 parts by mass.

[0216] Comparative Example 13

[0217] An anti-fog, antibacterial, and antistatic coating, compared to Example 1, does not contain heptadecafluorodecyltriethoxysilane-modified hollow titanium dioxide particles during the preparation of the anti-fog and antibacterial coating.

[0218] Comparative Example 14

[0219] An anti-fog, antibacterial, and antistatic coating, compared with Example 1, wherein the amount of 2-hydroxy-2-methyl-1-phenyl-1-propanone added is 10 parts by mass when preparing the anti-fog and antibacterial coating.

[0220] Comparative Example 15

[0221] An anti-fog, antibacterial, and antistatic coating is provided, with a thickness of 8 μm compared to Example 1.

[0222] Experimental Example

[0223] The anti-fogging performance, antibacterial performance, antistatic performance, transmittance, haze, pencil hardness, adhesion, and abrasion resistance of the materials prepared in Examples 1-15 and Comparative Examples 1-15 were tested respectively. The anti-fogging performance was tested according to GB / T 31726-2015 "Test Method for Antifogging of Plastic Films"; the antibacterial performance against Escherichia coli was tested according to GB / T 21866-2008 "Determination of Antibacterial Properties and Antibacterial Effect of Antibacterial Coatings (Films)"; the antistatic performance was tested according to GB / T 1410-2006 "Test Method for Volume Resistivity and Surface Resistance of Solid Insulating Materials"; the transmittance and haze were tested according to JIS K7105-1981 "Test Method for Optical Properties of Plastics"; the pencil hardness was tested according to JIS K5400-1990 "Determination of Adhesion Properties of Powder Coatings"; and the abrasion resistance was tested according to GB... According to the standard 1720-1979 "Determination of Adhesion of Paint Films", the adhesion of HC was tested, where 100 / 100 represents no film peeling and 90 / 100 represents 10% peeling. The abrasion resistance of the film was tested according to HG / T 4303-2012 "Determination of Abrasion Resistance of Surface-Hardened Polyester Films", using 0000# steel wool, 500 / 750 gf / cm². 2 The abrasion resistance of the film was determined by testing the maximum number of abrasion cycles without scratches on the film surface. The higher the number of abrasion cycles, the better the effect. The test results of various properties of the anti-fog, antibacterial and antistatic coatings are shown in Table 1.

[0224] Table 1

[0225]

[0226]

[0227] As shown in Table 1, the results of Examples 1, 2, 3, 11, 12 and Comparative Examples 11, 12, 13 indicate that the hollow titanium dioxide modified with fluorinated siloxane in the anti-fog, antibacterial, and antistatic coating can be uniformly distributed in the coating. Furthermore, the low surface energy fluorine atoms can spontaneously drive the titanium dioxide to migrate towards the film surface, further improving the anti-fog performance of the coating. The results of Example 13 show that UV prepolymers with more hydrophilic functional groups in the anti-fog and antibacterial coating exhibit better anti-fog performance. The results of Example 15 and Comparative Example 15 show that a thicker anti-fog and antibacterial coating results in a more stable hydrophilic coating and a better anti-fog effect.

[0228] The results of Example 9 and Comparative Example 8 show that the higher the content of allyl alkyl imidazole bromide salt prepolymer in the anti-fog and antibacterial coating, the more obvious the antibacterial effect. Analysis of the results of Example 8 and Comparative Example 7 shows that, secondly, within a certain number of carbon atoms, the alkyl chain length in the allyl alkyl imidazole bromide salt prepolymer is more effective at inhibiting the imidazole cations due to the higher carbon atom count. However, when the number of carbon atoms is too high, the alkyl chains become physically entangled, hindering the movement of the imidazole cations. Analysis of the results of Example 15 and Comparative Example 15 shows that the thicker the anti-fog and antibacterial coating, the higher the content of antibacterial imidazole bromide salt, and the better the antibacterial performance.

[0229] Analysis of the results from Examples 6 and 7 and Comparative Examples 1, 4, 5, and 6 shows that the higher the content of the antistatic agent in the antistatic primer or the thicker the antistatic primer, the better the antistatic effect. Analysis of the results from Examples 4 and 5 shows that the large π conjugated structure in the dual-curing resin also affects the antistatic effect of the coating. Analysis of the experimental results from Examples 8 and Comparative Example 7 shows that the presence of C=N and -N+- in the antifogging and antibacterial coating also affects the antistatic effect.

[0230] Furthermore, analysis of the results from Examples 10 and 14 and Comparative Examples 2, 3, 9, 10, and 14 shows that the initiator content in the coating also affects the degree of curing. Insufficient initiator content results in incomplete curing, while excessive initiator causes initiator precipitation. The completeness of curing directly affects all properties of the coating.

[0231] The present invention has been described according to the above embodiments. It should be understood that the above embodiments do not limit the present invention in any way. All technical solutions obtained by equivalent substitution or equivalent transformation fall within the scope of the present invention.

Claims

1. An anti-fogging, antibacterial, and antistatic coating, characterized in that, From bottom to top, the layers are: a substrate layer, an antistatic primer layer, and an anti-fog and antibacterial coating layer. The substrate layer is made of thermoplastic polyurethane, polyethylene terephthalate, or cellulose triacetate. The antistatic primer layer comprises the following raw materials in parts by weight: 5-15 parts of a dual-curing prepolymer, 7.5-22.5 parts of an reactive diluent, 1-5 parts of a first photoinitiator, 1-5 parts of a thermal initiator, 0.2-0.8 parts of an antistatic agent, and 51.7-85.3 parts of a first solvent. The anti-fog and antibacterial coating comprises the following raw materials in parts by weight: 15-20 parts of an allyl alkyl imidazolium bromide prepolymer, 5-10 parts of modified inorganic particles, 30-40 parts of a hydrophilic UV prepolymer, 1-5 parts of a second photoinitiator, and 25-49 parts of a second solvent. The allyl alkyl imidazolium bromide prepolymer was prepared by the following steps: 1-Allylimidazolium and bromoalkane were added to a container in a molar ratio of 1:2, followed by the addition of an organic solvent. The mixture was stirred at 60°C for 24 hours under an inert atmosphere. After cooling to room temperature, the mixture was rotary evaporated, washed with butanone, and dried in an oven at 60°C to constant weight to obtain the allylalkylimidazolium salt monomer. The allylalkylimidazolium salt monomer, 1,3-diallylimidazolium bromide, 2,4,6-trienylpropoxy-1,3,5-triazine, and pentaerythritol tetrakis(3-mercaptopropionic acid) ester were mixed in a molar ratio of 1:1~2:1~2:5, dissolved in a solvent, and then 0.5~1wt% of a photoinitiator containing pure solids was added. After irradiation with ultraviolet light, the product was obtained. The bromoalkane is bromooctane, bromodecane, bromododecane, or bromotetradecane.

2. The anti-fogging, antibacterial, and antistatic coating as described in claim 1, characterized in that: The substrate layer is made of thermoplastic polyurethane; the antistatic primer layer comprises the following raw materials in parts by weight: 12 parts of dual-curing prepolymer, 20 parts of reactive diluent, 3 parts of first photoinitiator, 3 parts of thermal initiator, 0.5 parts of antistatic agent, and 61.5 parts of first solvent; the antifog and antibacterial coating comprises the following raw materials in parts by weight: 15 parts of allyl alkyl imidazole bromide prepolymer, 5 parts of modified inorganic particles, 30 parts of hydrophilic UV prepolymer, 5 parts of second photoinitiator, and 45 parts of second solvent.

3. The anti-fogging, antibacterial, and antistatic coating as described in any one of claims 1 to 2, characterized in that: The dual-cured prepolymer is an aliphatic polyurethane acrylate containing -NCO groups; the reactive diluent is pentaerythritol triacrylate or trimethylolpropane triacrylate; the first photoinitiator and the second photoinitiator are 1-hydroxy-cyclohexylbenzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, liquid α-hydroxy ketone composite photoinitiator, or methyl benzoylformate, respectively; the thermal initiator is benzoyl peroxide or bislauroyl peroxide; the antistatic agent is hexadecyl dimethyl quaternary ammonium nitrate; the first solvent and the second solvent are one or a mixture of two of ethylene glycol monoethyl ether, propylene glycol methyl ether, isopropanol, and N,N-dimethylformamide in a 1:1 mass ratio.

4. The anti-fogging, antibacterial, and antistatic coating as described in any one of claims 1 to 2, characterized in that: The modified inorganic particles are modified hollow titanium dioxide with fluorinated siloxanes on their surface; the fluorinated siloxanes are tridecafluorooctyltriethoxysilane or heptadecafluorodecyltriethoxysilane; the modified inorganic particles are prepared through the following steps: Hollow titanium dioxide and hydrogen peroxide were mixed at a mass ratio of 1:3, sonicated for 20-40 min, refluxed at 75-85℃ for 3-5 h, filtered, washed with water, and then vacuum dried at 70-90℃ to constant weight to obtain hydroxylated hollow titanium dioxide. Anhydrous ethanol and water were mixed at a volume ratio of 100:1-3 to prepare an alcohol-water solution. The alcohol-water solution was mixed with the hydroxylated hollow titanium dioxide and sonicated for 15-25 min. Then, a fluorosiloxane was added, and the mixture was magnetically stirred at 55-65℃ for 2.5-3.5 h. After filtration, washing with water, and drying at 70-90℃ to constant weight, the final product was obtained.

5. The anti-fogging, antibacterial, and antistatic coating as described in any one of claims 1 to 2, characterized in that: The hydrophilic UV prepolymer is Changxing DR-W470, Changxing DR-W450, Bayer UV LS2282, Bayer UV LS2317, BASF LR8949 or BASF LR9005.

6. The anti-fogging, antibacterial, and antistatic coating as described in any one of claims 1 to 2, characterized in that: The thickness of the substrate layer is 25~250μm; the thickness of the antistatic primer layer is 90~120nm; and the thickness of the anti-fog and antibacterial coating layer is 2~5μm.

7. The method for preparing the anti-fogging, antibacterial, and antistatic coating according to any one of claims 1 to 6, characterized in that, Includes the following steps: (1) Mix the first solvent, the double-cured prepolymer and the reactive diluent, stir at 500~800 r / min for 30 min, add the antistatic agent, stir at 500~800 r / min for 5 min, add the first photoinitiator, stir at 500~800 r / min for 5 min, add the thermal initiator, stir at 500~800 r / min for 5 min, and finally stir at 800~1000 r / min for 15 min. Filter with a 1 μm filter to obtain the antistatic coating liquid. (2) Mix the second solvent, allyl alkyl imidazole bromide prepolymer and hydrophilic UV prepolymer, stir at 500~800 r / min for 30 min, add modified inorganic particles and stir at 800~1000 r / min for 30 min, then add the second photoinitiator and stir at 800~1000 r / min for 15 min, filter with a 1 μm filter element to obtain anti-fog antibacterial coating liquid; (3) Apply antistatic coating liquid to the substrate layer using micro-gravure coating process, dry at 100℃ for 1 min, and then irradiate with 500mJ / cm² ultraviolet light to obtain antistatic base layer. (4) Apply anti-fogging and antibacterial coating liquid to the surface of the antistatic base layer using micro-concave, slit or scraper coating process, dry at 90℃ for 2 min, and then irradiate with 500mJ / cm² ultraviolet light to obtain anti-fogging, antibacterial and antistatic coating.

8. The application of the anti-fog, antibacterial, and antistatic coating according to any one of claims 1 to 6 in the preparation of a mirror protective layer.

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