An organic-inorganic hybrid wear-resistant anti-fog coating, a preparation method and application thereof, and an organic-inorganic hybrid wear-resistant anti-fog coating layer

Abstract

The present application relates to the technical field of material modification, and particularly relates to an organic-inorganic hybrid wear-resistant anti-fog coating, a preparation method and application thereof, and an organic-inorganic hybrid wear-resistant anti-fog coating layer. The preparation method of the organic-inorganic hybrid wear-resistant anti-fog coating provided by the present application comprises the following steps: hydrolyzing amino silane, mixing the obtained hydrolyzed amino silane with a silica dispersion solution, and performing first heating to obtain aminosilica; mixing the aminosilica, propenesulfonic acid lactone and a first solvent, and performing second heating to obtain zwitterion modified nanosilica balls; and mixing the zwitterion modified nanosilica balls, silica sol, titanium dioxide, a crosslinking agent, a photoinitiator and a second solvent to obtain the organic-inorganic hybrid wear-resistant anti-fog coating. The organic-inorganic hybrid wear-resistant anti-fog coating prepared by the preparation method has excellent hydrophilic effect and excellent comprehensive performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of material modification, and particularly relates to an organic-inorganic hybrid wear-resistant anti-fog coating, a preparation method and application thereof, and an organic-inorganic hybrid wear-resistant anti-fog coating. BACKGROUND

[0002] Fogging on the surface of optical equipment not only reduces visibility, but also causes light scattering and reduces light flux due to the attachment of condensed water droplets on the surface of the base material, thereby affecting the clarity of imaging of the optical device. In addition to fogging caused by temperature and humidity changes, dust and pollutants in the air are easily adsorbed on the surface of the device under the action of static electricity, thereby hindering the normal operation of the device. It is of great importance to develop a functional coating with anti-fog and self-cleaning effects to meet the display requirements. SUMMARY

[0003] Therefore, the present application aims to provide an organic-inorganic hybrid wear-resistant anti-fog coating, a preparation method and application thereof, and an organic-inorganic hybrid wear-resistant anti-fog coating. The organic-inorganic hybrid wear-resistant anti-fog coating prepared by the preparation method has excellent hydrophilic effect, and also has excellent wear resistance, water resistance, anti-static and other comprehensive properties.

[0004] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions:

[0005] The present application provides a preparation method of an organic-inorganic hybrid wear-resistant anti-fog coating, comprising the following steps:

[0006] After the amino silane is hydrolyzed, the hydrolyzed amino silane is mixed with a silica dispersion liquid to perform first heating, so as to obtain amino-modified silicon dioxide;

[0007] The amino-modified silicon dioxide, propenesulfonic acid lactone and a first solvent are mixed to perform second heating, so as to obtain zwitterion-modified nanometer silicon dioxide balls;

[0008] The zwitterion-modified nanometer silicon dioxide balls, silica sol, titanium dioxide, a crosslinking agent, a photoinitiator and a second solvent are mixed, so as to obtain the organic-inorganic hybrid wear-resistant anti-fog coating.

[0009] Preferably, the hydrolysis process comprises: mixing the amino silane, water and ethanol, and then performing hydrolysis under acidic conditions;

[0010] The amino silane comprises one or more of N-aminoethyl-gamma-aminopropyltrimethoxysilane, N,N-dimethyl-3-aminopropyltrimethoxysilane, N,N-diethyl-3-(trimethoxysilyl)propylamine, phenylaminomethyltriethoxysilane, gamma-aminopropyltriethoxysilane and polyaminoalkyltrialkoxysilane;

[0011] The mass ratio of the amino silane, water and ethanol is (10-40):(2-15):(50-100);

[0012] The pH value of the acidic condition is 2-6; the acid liquid for providing the acidic condition is one or more of acetic acid, nitric acid and hydrochloric acid, and the mass percentage concentration of the acid liquid is 30%-40%;

[0013] The temperature of the hydrolysis is 15-25℃, and the time is 1-5h.

[0014] Preferably, the silica dispersion liquid comprises silica nanoparticles and an aqueous ethanol solution;

[0015] The mass ratio of the silica nanoparticles and the aqueous ethanol solution is 1:(10-40);

[0016] The volume ratio of ethanol and water in the aqueous ethanol solution is preferably (1-5):1;

[0017] The mass ratio of the amino silane after the hydrolysis and the silica nanoparticles is (1-4):1;

[0018] The temperature of the first heating is 60℃, and the time is 4-8h.

[0019] Preferably, the mass ratio of the aminated silica and propylene sulfite is (1-3):1;

[0020] The mass ratio of the total mass of the aminated silica and propylene sulfite and the first solvent is 1:(2-5);

[0021] The first solvent comprises one or more of acetone, acetonitrile, toluene, diethyl ether and methanol;

[0022] The temperature of the second heating is 80℃, and the time is 4-8h.

[0023] Preferably, the preparation method of the silica sol comprises: mixing tetraethyl orthosilicate, alcohol, water and inorganic acid, and sequentially performing hydrolysis and standing aging to obtain the silica sol;

[0024] The volume ratio of the tetraethyl orthosilicate, alcohol, water and inorganic acid is (1-5):(12-20):(0.5-1.5):0.1;

[0025] The alcohol comprises ethanol and / or propanol;

[0026] The mass percentage concentration of the inorganic acid is 20-40%, and the inorganic acid is nitric acid or hydrochloric acid;

[0027] The temperature of the hydrolysis is 20-25℃, and the time is 1-6h;

[0028] The temperature of the standing aging is room temperature, and the time is 1-3 days.

[0029] The mass ratio of the amphoteric ion modified nanosilica sphere to the silica sol is 100:(1-10).

[0030] Preferably, the crosslinking agent is an acrylate crosslinking agent.

[0031] The mass ratio of the amphoteric ion modified nanosilica sphere to the crosslinking agent is (10-100):1.

[0032] The photoinitiator includes one or more of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-methylphenylpropane-1-ketone, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide and benzophenone.

[0033] The mass ratio of the amphoteric ion modified nanosilica sphere to the photoinitiator is (50-200):1.

[0034] The titanium dioxide is a nanometer titanium dioxide colloid, and the mass ratio of the nanometer titanium dioxide colloid to the silica sol is (1-3):1.

[0035] The second solvent includes ethanol and water with a mass ratio of 1:(1-5).

[0036] The application also provides an organic-inorganic hybrid wear-resistant anti-fog coating prepared by the preparation method.

[0037] The application also provides application of the organic-inorganic hybrid wear-resistant anti-fog coating in preparation of an organic-inorganic hybrid wear-resistant anti-fog coating layer.

[0038] The application also provides a preparation method of an organic-inorganic hybrid wear-resistant anti-fog coating layer.

[0039] After the organic-inorganic hybrid wear-resistant anti-fog coating is coated on the surface of the substrate by the dip-coating method, UV curing is performed to obtain the organic-inorganic hybrid wear-resistant anti-fog coating layer.

[0040] The organic-inorganic hybrid wear-resistant anti-fog coating is the organic-inorganic hybrid wear-resistant anti-fog coating as described above.

[0041] Preferably, the pulling speed of the dip-coating method is 10-200 mm / min.

[0042] The wavelength of the light irradiation for the UV curing is 365 nm, and the light irradiation intensity is 180-210 mW / cm 2, the illumination time is 1-3h, and the illumination temperature is room temperature.

[0043] The application provides a preparation method of an organic-inorganic hybrid wear-resistant anti-fog coating, and comprises the following steps: mixing and performing first heating on hydrolyzed amino silane and a silicon dioxide dispersion solution to obtain amino-modified silicon dioxide; mixing and performing second heating on the amino-modified silicon dioxide, propene sultone and a first solvent to obtain zwitterion-modified nanometer silicon dioxide balls; and mixing the zwitterion-modified nanometer silicon dioxide balls, silica sol, titanium dioxide, a crosslinking agent, a photoinitiator and a second solvent to obtain the organic-inorganic hybrid wear-resistant anti-fog coating. The zwitterion modification of the nanometer silicon dioxide balls can enhance the hydrophilicity and antistatic property of the nanometer silicon dioxide balls, the titanium dioxide can photocatalytically degrade pollutants to improve the weather resistance of the coating and maintain the long-acting hydrophilic effect of the coating surface; meanwhile, the inorganic silica sol has the characteristics of high bonding strength with the substrate, can form strong bonding force with the surface of most materials and enhance the water resistance of the coating, the acrylic crosslinking agent provides an organic crosslinking network to improve the film-forming property and mechanical strength of the coating, and the high strength and strong hydrophilicity of the above-mentioned organic-inorganic components complement each other to provide protection for the wear resistance, anti-fog property and antistatic property of the coating.

[0044] The application further provides a preparation method of an organic-inorganic hybrid wear-resistant anti-fog coating, comprising the following steps: coating an organic-inorganic hybrid wear-resistant anti-fog coating on the surface of a substrate by using the dip-coating method, and then performing UV curing to obtain the organic-inorganic hybrid wear-resistant anti-fog coating. The prepared organic-inorganic hybrid wear-resistant anti-fog coating comprises silica sol with high bonding strength and titanium dioxide capable of absorbing ultraviolet rays, thus overcoming the defects of poor stability and poor aging resistance of an organic hydrophilic coating, and having the advantages of wear resistance, antistatic property, anti-fog property and water resistance, and the production process is simple and can meet the actual application requirements. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1 The static contact angle diagram (a) of the glass sheet modified with the organic-inorganic hybrid wear-resistant anti-fog coating and the static contact angle diagram (b) of a blank glass sheet according to Example 1;

[0046] Figure 2 The SEM diagram of the zwitterion-modified nanometer silicon dioxide balls according to Example 1;

[0047] Figure 3 The actual object diagram of the glass sheet modified with the organic-inorganic hybrid wear-resistant anti-fog coating and the blank glass sheet according to Example 1, which are placed in a 60℃ water bath for 0h, 3h and 12h;

[0048] Figure 4Antistatic diagram of blank PET film and PET film modified with the organic-inorganic hybrid abrasion-resistant anti-fog coating described in Example 1;

[0049] Figure 5 Contact angle of the glass modified with the organic-inorganic hybrid abrasion-resistant anti-fog coating described in Example 1 soaked in water for different time;

[0050] Figure 6 Abrasion-resistant test results of the glass modified with the organic-inorganic hybrid abrasion-resistant anti-fog coating described in Example 1.

[0051] Figure 7 Anti-fog pictures and contact angle of the glass modified with the organic-inorganic hybrid abrasion-resistant anti-fog coating described in Example 1, 2, 3, 4 after abrasion. DETAILED DESCRIPTION

[0052] The present application provides a preparation method of an organic-inorganic hybrid abrasion-resistant anti-fog coating, comprising the following steps:

[0053] After hydrolysis of the amino silane, the obtained hydrolyzed amino silane is mixed with a silica dispersion liquid to perform first heating, to obtain amino-silica;

[0054] The amino-silica, propenesulfonic acid lactone and a first solvent are mixed to perform second heating, to obtain zwitterion-modified nanometer silica spheres;

[0055] The zwitterion-modified nanometer silica spheres, silica sol, titanium dioxide, crosslinking agent, photoinitiator and a second solvent are mixed, to obtain the organic-inorganic hybrid abrasion-resistant anti-fog coating.

[0056] In the present application, all the raw materials for preparation are commercially available products well known to those skilled in the art, unless otherwise specified.

[0057] In the present application, after hydrolysis of the amino silane, the obtained hydrolyzed amino silane is mixed with a silica dispersion liquid to perform first heating, to obtain amino-silica.

[0058] In the present application, the process of hydrolysis preferably comprises: mixing the amino silane, water and ethanol, and then performing hydrolysis under acidic conditions.

[0059] In the present application, the amino silane preferably includes one or more of N-aminoethyl-γ-aminopropyl trimethoxysilane, N,N-dimethyl-3-aminopropyl trimethoxysilane (KH556), N,N-diethyl-3-(trimethoxysilyl)propylamine, phenylaminomethyl triethoxysilane, γ-aminopropyl triethoxysilane, and polyaminoalkyl trialkoxysilane; when the amino silane is two or more of the above specific choices, the present application does not have any special limitation on the ratio of the above specific substances, and mixing in any ratio can be used. In the embodiments of the present application, the amino silane can be N,N-dimethyl-3-aminopropyl trimethoxysilane.

[0060] In the present application, the mass ratio of the amino silane, water, and ethanol is preferably (10-40):(2-15):(50-100), and more preferably (20-40):(2-10):(50-80). In the embodiments of the present application, the mass ratio of the amino silane, water, and ethanol can be 25:8:80, 20:8:70, 20:6:80, or 20:6:80.

[0061] In the present application, the pH value of the acidic condition is preferably 2-6, and more preferably 3-5. The acidic condition is preferably provided by an acid solution, and the mass percentage concentration of the acid solution is preferably 30%-40%, and more preferably 35%-38%. In the present application, the acid solution is preferably one or more of acetic acid, nitric acid, and hydrochloric acid, and more preferably hydrochloric acid; when the acid solution is two or more of the above specific choices, the present application does not have any special limitation on the ratio of the above specific substances, and mixing in any ratio can be used. In the embodiments of the present application, the pH value of the acidic condition can be 4; and the acid solution can be hydrochloric acid with a mass percentage concentration of 36%.

[0062] In the present application, the temperature of the hydrolysis is preferably 15-25°C, and more preferably 20-25°C; and the time of the hydrolysis is preferably 1-5h, and more preferably 1-3h. In the present application, the hydrolysis is preferably performed under stirring, and the present application does not have any special limitation on the process of the stirring, and a process well known to those skilled in the art can be used. In the embodiments of the present application, the temperature of the hydrolysis can be 21°C, and the time can be 1h.

[0063] After the hydrolysis is completed, the present application also preferably includes standing, and the present application does not have any special limitation on the process of the standing, and a process well known to those skilled in the art can be used.

[0064] In the present application, the silica dispersion solution preferably comprises silica nanoparticles and an aqueous ethanol solution; the mass ratio of the silica nanoparticles and the aqueous ethanol solution is preferably 1:(10-40), more preferably 1:(15-35). In the present application, the volume ratio of ethanol and water in the aqueous ethanol solution is preferably (1-5):1, more preferably (1-3):1. In the embodiments of the present application, the mass ratio of the silica nanoparticles and the aqueous ethanol solution can be 1:27, 1:32 or 1:18; the volume ratio of ethanol and water in the aqueous ethanol solution can be 1:1 or 1.5:1.

[0065] In the present application, the mass ratio of the hydrolyzed amino silane and the silica is preferably (1-4):1, more preferably (2-3):1; the temperature of the first heating is preferably 60°C; the time is preferably 4-8h, more preferably 4-6h. In the embodiments of the present application, the mass ratio of the hydrolyzed amino silane and the silica can be 2:1, 2.5:1 or 4:3; the temperature of the first heating can be 60°C, and the time can be 5h.

[0066] After obtaining the aminated silica, the present application mixes the aminated silica, propene sultone and a first solvent for a second heating to obtain the zwitterion-modified nanosilica spheres.

[0067] In the present application, the mass ratio of the aminated silica and propene sultone is preferably (1-3):1, more preferably (1-2):1. In the embodiments of the present application, the mass ratio of the aminated silica and propene sultone can be 1.5:1, 4:3 or 1:1.

[0068] In the present application, the ratio of the total mass of the aminated silica and propene sultone to the mass of the first solvent is preferably 1:(2-5), more preferably 1:(4-5). In the embodiments of the present application, the ratio of the total mass of the aminated silica and propene sultone to the mass of the first solvent can be 1:5 or 7:30.

[0069] In the present application, the first solvent preferably comprises one or more of acetone, acetonitrile, toluene, diethyl ether and methanol, more preferably methanol; when the first solvent is two or more of the above specific choices, the present application does not have any special limitation on the ratio of the above specific substances, and mixing in any ratio can be performed. In the embodiments of the present application, the solvent can be methanol.

[0070] The present application does not have any special limitation on the process of the mixing, and any process known to those skilled in the art can be used.

[0071] In the present application, the temperature of the second heating is preferably 80℃; the time is preferably 4-8h, more preferably 5-8h. In the embodiment of the present application, the time of the second heating can be 6h.

[0072] After the second heating is completed, the present application further preferably comprises washing and drying in sequence, and the present application does not have any special limitation on the process of the washing and drying, which can be performed by using the process well known to those skilled in the art.

[0073] After the zwitterion-modified nanosilica spheres are obtained, the zwitterion-modified nanosilica spheres, silica sol, titanium dioxide, crosslinking agent, photoinitiator and second solvent are mixed to obtain the organic-inorganic hybrid wear-resistant anti-fog coating.

[0074] In the present application, the mass ratio of the zwitterion-modified nanosilica spheres to the silica sol is preferably 100:(1-10), more preferably 100:(1-5). In the embodiment of the present application, the mass ratio of the zwitterion-modified nanosilica spheres to the silica sol can be 100:1 or 100:2 or 100:5.

[0075] In the present application, the preparation method of the silica sol preferably comprises mixing tetraethyl orthosilicate, alcohol, water and inorganic acid, and then performing hydrolysis and standing and aging in sequence to obtain the silica sol.

[0076] In the present application, the volume ratio of the tetraethyl orthosilicate, alcohol, water and inorganic acid is preferably (1-5):(12-20):(0.5-1.5):0.1, more preferably (2-5):(12-15):1:0.1, most preferably (2-3):(12-13):1:0.1. In the embodiment of the present application, the volume ratio of the tetraethyl orthosilicate, alcohol, water and inorganic acid can be 12:2:0.3:0.1, 12:2:1:0.1 or 12:4:1:0.1.

[0077] In the present application, the alcohol preferably comprises ethanol and / or propanol, more preferably ethanol, and when the alcohol is ethanol and propanol, the present application does not have any special limitation on the amount of the ethanol and propanol, which can be performed by using the process well known to those skilled in the art. In the embodiment of the present application, the alcohol can be ethanol.

[0078] In the present application, the mass percentage concentration of the inorganic acid is preferably 20-40%, more preferably 30-40%. In the present application, the type of the inorganic acid is preferably nitric acid or hydrochloric acid.

[0079] The present application does not have any special limitation on the mixing process, which can be performed by using the process well known to those skilled in the art.

[0080] In the present application, the temperature of the hydrolysis is preferably 20-25°C; the time is preferably 1-6h, more preferably 1-3h. In the present application, the hydrolysis is preferably carried out under stirring, and the present application does not have any special limitation on the process of the stirring, which can be carried out by using the process well known to those skilled in the art. In the embodiments of the present application, the temperature of the hydrolysis can be 25°C, and the time can be 1h.

[0081] In the present application, the temperature of the standing aging is preferably room temperature, and the time of the standing aging is preferably 1-3 days, more preferably 1-2 days. In the embodiments of the present application, the time of the standing aging can be 2 days.

[0082] In the present application, the tetraethyl orthosilicate is hydrolyzed in an acidic environment to obtain a silica sol.

[0083] In the present application, the titanium dioxide is preferably a nano-titanium dioxide colloid; the particle size of the titanium dioxide in the nano-titanium dioxide colloid is preferably 5nm. In the present application, the titanium dioxide colloid is preferably anatase titanium dioxide with a solid content of 20±1% and a crystalline form of 100%.

[0084] In the present application, the mass ratio of the nano-titanium dioxide colloid to the silica sol is preferably (1-3):1, more preferably (2-3):1. In the embodiments of the present application, the mass ratio of the nano-titanium dioxide colloid to the silica sol can be 2:1 or 2.5:1.

[0085] In the present application, the crosslinking agent is preferably an acrylate crosslinking agent, more preferably one or more of ethylene glycol dimethacrylate, pentaerythritol triacrylate and pentaerythritol hexaacrylate. When the crosslinking agent is two or more of the above specific choices, the present application does not have any special limitation on the ratio of the above specific substances, which can be mixed in any ratio. In the embodiments of the present application, the crosslinking agent can be pentaerythritol triacrylate or ethylene glycol dimethacrylate.

[0086] In the present application, the mass ratio of the zwitterion-modified nano-silica spheres to the crosslinking agent is preferably (10-100):1, more preferably (50-100):1. In the embodiments of the present application, the mass ratio of the zwitterion-modified nano-silica spheres to the crosslinking agent can be 50:1 or 100:1.

[0087] In the present application, the photoinitiator preferably includes one or several of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone (UV-2959), 1-hydroxycyclohexyl phenyl ketone (UV-184), 2-hydroxy-methylphenylpropan-1-one, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide and benzophenone (BP), and the present application does not have any special limitation on the ratio of the above-mentioned specific substances when the photoinitiator is two or more of the above-mentioned specific selection, and the mixing can be carried out in any ratio. In the embodiment of the present application, the photoinitiator can be UV-184, UV-2959 or BP.

[0088] In the present application, the mass ratio of the zwitterion-modified nanosilica sphere and the photoinitiator is preferably (50-200):1, and more preferably (100-200):1. In the embodiment of the present application, the mass ratio of the zwitterion-modified nanosilica sphere and the photoinitiator can be 100:1.

[0089] In the present application, the second solvent preferably includes ethanol and water, and the mass ratio of the ethanol and water is preferably 1:(1-5), and more preferably 1:(1-3). In the embodiment of the present application, the mass ratio of the ethanol and water can be 1:1.

[0090] The present application does not have any special limitation on the process of the mixing, and the process known to those skilled in the art can be used.

[0091] The present application also provides an organic-inorganic hybrid wear-resistant anti-fog coating prepared by the preparation method.

[0092] The present application also provides the application of the organic-inorganic hybrid wear-resistant anti-fog coating in the preparation of an organic-inorganic hybrid wear-resistant anti-fog coating layer.

[0093] The present application also provides a preparation method of an organic-inorganic hybrid wear-resistant anti-fog coating layer, which comprises the following steps:

[0094] After coating the organic-inorganic hybrid wear-resistant anti-fog coating on the surface of the substrate by the dip-coating method, UV curing is performed to obtain the organic-inorganic hybrid wear-resistant anti-fog coating layer.

[0095] The present application does not have any special limitation on the material of the substrate, and the material known to those skilled in the art can be used.

[0096] Before the coating, the present application preferably pretreats the substrate, and the pretreatment preferably includes cleaning, and the present application does not have any special limitation on the process of the cleaning, and the process known to those skilled in the art can be used.

[0097] In the present application, the pulling speed of the dip-coating method is preferably 10-200 mm / min, more preferably 10-100 mm / min. In the embodiment of the present application, the pulling speed of the dip-coating method can be 60 mm / min.

[0098] In the present application, the wavelength of the light irradiation for the UV curing is preferably 365 nm, the light irradiation intensity is preferably 180-210 mW / cm 2 , the light irradiation time is preferably 1-3 h, and the light irradiation temperature is preferably room temperature. In the embodiment of the present application, the wavelength of the light irradiation for the UV curing can be 365 nm, the light irradiation intensity can be 210 mW / cm 2 , the light irradiation time can be 1 h, and the light irradiation temperature can be room temperature.

[0099] The technical solutions in the present application will be described clearly and completely in combination with the embodiments in the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0100] Embodiment 1

[0101] 12 mL of ethanol, 2 mL of tetraethyl orthosilicate, 1 mL of water and 0.1 mL of 40% mass concentration nitric acid were mixed, stirred at 25°C for 1 h, and then aged for 2 days to obtain a silica sol;

[0102] KH556, water and ethanol were mixed in a mass ratio of 25:8:80, and then adjusted to a pH value of 4 by using 36% mass percent hydrochloric acid. After stirring for 1 h, the hydrolyzed KH556 was obtained by standing;

[0103] After 10 g of silica nanoparticles were ultrasonically dispersed in a mixture of 150 mL of water and 150 mL of ethanol, 20 g of the hydrolyzed KH556 was added, and the mixture was reacted at 60°C for 5 h, and then dried to obtain aminated silica;

[0104] 3 g of the aminated silica and 3 g of propenesulfonic acid lactone were dissolved in 30 g of methanol, and the mixture was heated at 80°C for 6 h. After the product was washed with ethanol and dried, the zwitterionic modified nanosilica spheres were obtained;

[0105] The amphoteric ion modified nanosilica, nanometer titanium dioxide colloid (particle size of titanium dioxide is 5 nm, solid content is 20±1%, and crystal form is 100% anatase), the silica sol, pentaerythritol triacrylate, UV-184, ethanol and water are mixed uniformly according to a mass ratio of 10:0.2:0.1:0.1:0.1:100:100 to obtain an organic-inorganic hybrid wear-resistant anti-fog coating;

[0106] The cleaned glass sheet is immersed in the organic-inorganic hybrid wear-resistant anti-fog coating, pulled out by a pulling machine at a speed of 60 mm / min, and then subjected to UV irradiation at a wavelength of 365 nm and an illumination intensity of 210 mW / cm 2 for 1 h at room temperature to obtain a glass sheet modified with an organic-inorganic hybrid wear-resistant anti-fog coating;

[0107] Or the PET film is cleaned with ethanol by ultrasonic cleaning, and then immersed in the organic-inorganic hybrid wear-resistant anti-fog coating after plasma cleaning for 3-5 min, and the coating is coated and ultraviolet cured in the same way to obtain a PET film modified with an organic-inorganic hybrid wear-resistant anti-fog coating.

[0108] Figure 1 The static contact angle diagram of the glass sheet modified with the organic-inorganic hybrid wear-resistant anti-fog coating (a) and the static contact angle diagram of the blank glass sheet (b) are shown in Figure 1 It can be seen that the surface contact angle of the organic-inorganic hybrid wear-resistant anti-fog coating of the glass sheet modified with the organic-inorganic hybrid wear-resistant anti-fog coating according to Example 1 is 2°, and the surface contact angle of the blank glass sheet is 17°;

[0109] Figure 2 The SEM diagram of the amphoteric ion modified nanosilica spheres is shown in Figure 2 It can be seen that the modified silica spheres have regular morphology, and the average particle size is about 200 nm;

[0110] The glass sheet modified with the organic-inorganic hybrid wear-resistant anti-fog coating according to Example 1 and the blank glass sheet are placed in a 60°C water bath at the same time for 0 h, 3 h and 12 h, and the actual diagram is shown in Figure 3 (in which ① is the glass sheet modified with the organic-inorganic hybrid wear-resistant anti-fog coating according to Example 1, ② is the blank glass sheet) shown in Figure 3 It can be seen that the glass sheet modified with the organic-inorganic hybrid wear-resistant anti-fog coating according to Example 1 can quickly adsorb water droplets to spread into a transparent water film at the initial stage of anti-fogging, without affecting the line of sight of the substrate, while the blank glass surface will block the line of sight due to the aggregation of water droplets. After several hours, the surface of the glass sheet modified with the coating still maintains the anti-fogging effect and is transparent and free of fog, but the surface of the blank glass is blocked by light refraction due to the aggregation of small water droplets;

[0111] The blank PET film and the PET film modified with the organic-inorganic hybrid abrasion-resistant anti-fog coating described in Example 1 were respectively attached to a finger (as shown in Figure 4 After 30 cycles of reciprocating friction on the PTEE film at a constant speed with a force of about 1 N, the blank PET film surface adsorbed a large number of polystyrene foam balls, while the surface of the modified PET film did not adsorb foam balls, indicating good antistatic performance.

[0112] The glass sheet modified with the organic-inorganic hybrid abrasion-resistant anti-fog coating described in Example 1 was immersed in deionized water for 1, 3, 5, and 7 days, respectively, and then taken out and dried with nitrogen to remove surface water vapor, and the contact angle was measured. Among them, Figure 5 The contact angle of the glass sheet modified with the organic-inorganic hybrid abrasion-resistant anti-fog coating described in Example 1 after immersion in water for different times is shown in Figure 5 It can be seen that after 7 days of immersion, the contact angle of the glass sheet modified with the organic-inorganic hybrid abrasion-resistant anti-fog coating described in Example 1 increased from the initial 2° to 7°, still maintaining super-hydrophilic state.

[0113] The glass modified with the organic-inorganic hybrid abrasion-resistant anti-fog coating described in Example 1 was subjected to abrasion resistance test, Figure 6 The abrasion resistance test results of the glass modified with the organic-inorganic hybrid abrasion-resistant anti-fog coating described in Example 1 are shown in Figure 6 It can be seen that after 10,000 times of friction and abrasion, the contact angle of the coating surface increased by no more than 10 degrees, maintaining good wetting performance, and the coating had good abrasion resistance.

[0114] Example 2

[0115] 12 mL of ethanol, 4 mL of tetraethyl orthosilicate, 1 mL of water, and 0.1 mL of 40% mass percentage nitric acid were mixed, stirred at 25°C for 1 hour, and then allowed to stand for 2 days to obtain a silica sol;

[0116] KH556, water, and ethanol were mixed in a mass ratio of 20:8:70, and then adjusted to a pH of 4 with 36% mass percentage hydrochloric acid. After stirring at 21°C for 1 hour and standing, the hydrolyzed KH556 was obtained.

[0117] 10 g of silica nanoparticles were ultrasonically dispersed in a mixture of 200 mL of ethanol and 150 mL of water, and then 20 g of the hydrolyzed KH556 was added. The mixture was reacted at 60°C for 5 hours, and then dried to obtain aminated silica.

[0118] 4 g of the aminated silica and 3 g of propenesulfonic acid lactone were dissolved in 30 g of methanol, and then heated at 80°C for 6 hours. The product was washed with ethanol and then dried to obtain zwitterion-modified nanosilica spheres.

[0119] The amphoteric ion modified nano-silica, nano-titania colloid (particle size of titania is 5 nm, solid content is 20±1% of anatase type titania with 100% of crystalline form), the silica sol, pentaerythritol hexaacrylate, UV-2959, ethanol and water were mixed uniformly at a mass ratio of 10:0.5:0.2:0.1:0.1:100:100 to obtain an organic-inorganic hybrid wear-resistant anti-fog coating;

[0120] The cleaned glass sheet was immersed in the organic-inorganic hybrid wear-resistant anti-fog coating, pulled out by a pulling machine at a speed of 60 mm / min, and reacted at room temperature under UV light irradiation at a wavelength of 365 nm and an illumination intensity of 210 mW / cm 2 for 1 h to obtain a glass sheet modified with an organic-inorganic hybrid wear-resistant anti-fog coating.

[0121] The organic-inorganic hybrid wear-resistant anti-fog coating prepared in this example had similar lubricity, wear resistance and hydrophilicity to the results of Example 1.

[0122] Example 3

[0123] The silica sol was obtained by mixing 12 mL of ethanol, 2 mL of tetraethyl orthosilicate, 1 mL of water and 0.1 mL of 40% mass percent nitric acid, stirring at 25°C for 1 hour, and then standing for 2 days.

[0124] The hydrolyzed KH556 was obtained by mixing KH556, water and ethanol uniformly at a mass ratio of 20:6:80, adjusting the pH value to 4 with 36% mass percent hydrochloric acid, stirring at 21°C for 1 h, and then standing.

[0125] After the 10 g of silica nanoparticles were ultrasonically dispersed in a mixture of 150 mL of water and 150 mL of ethanol, 25 g of the hydrolyzed KH556 was added, and the mixture was reacted at 60°C for 5 h, and then dried to obtain aminated silica.

[0126] The amphoteric ion modified nano-silica was obtained by dissolving 4 g of the aminated silica and 3 g of propenesulfonic acid lactone in 30 g of methanol, heating at 80°C for 6 h, washing the product with ethanol, and then drying.

[0127] The amphoteric ion modified nano-silica, nano-titania colloid (particle size of titania is 5 nm, solid content is 20±1% of anatase type titania with 100% of crystalline form), the silica sol, pentaerythritol hexaacrylate, UV-2959, ethanol and water were mixed uniformly at a mass ratio of 10:0.5:0.2:0.1:0.1:100:100 to obtain an organic-inorganic hybrid wear-resistant anti-fog coating;

[0128] The cleaned glass sheet was immersed in the organic-inorganic hybrid abrasion-resistant anti-fog coating, pulled out by a pulling machine at a speed of 60 mm / min, and reacted under UV light with a wavelength of 365 nm and an illumination intensity of 210 mW / cm 2 at room temperature for 1 h to obtain a glass sheet modified with an organic-inorganic hybrid abrasion-resistant anti-fog coating.

[0129] The organic-inorganic hybrid abrasion-resistant anti-fog coating prepared in this example had similar lubricity, abrasion resistance and hydrophilicity to the results of Example 1.

[0130] Example 4

[0131] A mixture of 12 mL of ethanol, 2 mL of tetraethyl orthosilicate, 0.3 mL of water and 0.1 mL of 40% mass percent nitric acid was stirred at 25°C for 1 h, and then aged for 2 days to obtain a silica sol;

[0132] KH556, water and ethanol were mixed in a mass ratio of 20:6:80, and then adjusted to a pH of 4 with 36% mass percent hydrochloric acid. After stirring at 21°C for 1 h, the mixture was allowed to stand to obtain hydrolyzed KH556;

[0133] After 10 g of silica nanoparticles were ultrasonically dispersed in a mixture of 100 mL of water and 100 mL of ethanol, 20 g of the hydrolyzed KH556 was added, and the mixture was reacted at 60°C for 5 h and then dried to obtain aminated silica;

[0134] After 3 g of the aminated silica and 2 g of propenesulfonic acid lactone were dissolved in 25 g of methanol, the mixture was heated at 80°C for 6 h. After the product was washed with ethanol and dried, zwitterion-modified nanosilica spheres were obtained;

[0135] The zwitterion-modified nanosilica, nanotitanium dioxide colloid (titanium dioxide with a particle size of 5 nm, solid content of 20±1%, and 100% anatase type), the silica sol, pentaerythritol hexaacrylate, BP, ethanol and water were mixed in a mass ratio of 10:0.2:0.1:0.1:0.1:100:100 to obtain an organic-inorganic hybrid abrasion-resistant anti-fog coating;

[0136] The cleaned glass sheet was immersed in the organic-inorganic hybrid abrasion-resistant anti-fog coating, pulled out by a pulling machine at a speed of 60 mm / min, and reacted under UV light with a wavelength of 365 nm and an illumination intensity of 210 mW / cm 2 at room temperature for 1 h to obtain a glass sheet modified with an organic-inorganic hybrid abrasion-resistant anti-fog coating.

[0137] The lubricity, wear resistance, and hydrophilicity of the organic-inorganic hybrid wear-resistant and anti-fog coating prepared in this embodiment are similar to those in Example 1.

[0138] The glass modified with the organic-inorganic hybrid wear-resistant and anti-fog coating described in Examples 1, 2, 3, and 4 was subjected to 10,000 cycles of reciprocating rubbing under a 200g load. The contact angle of the coating surface was then tested, and the anti-fog effect was observed when the glass was placed in a 60°C water bath. Figure 7 ),Depend on Figure 7 It can be seen that the glass modified with organic-inorganic hybrid wear-resistant and anti-fog coatings as described in Examples 1, 2, 3, and 4 still retains hydrophilic properties after being rubbed, thus achieving an anti-fog effect. The coating has a certain wear resistance to meet the needs of practical applications.

[0139] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing an organic-inorganic hybrid abrasion-resistant anti-fog coating, characterized in that, Includes the following steps: An organic-inorganic hybrid wear-resistant and anti-fog coating is applied to the surface of a substrate using the dip-coating method and then UV cured to obtain the organic-inorganic hybrid wear-resistant and anti-fog coating. The preparation method of the organic-inorganic hybrid wear-resistant and anti-fog coating includes the following steps: After hydrolyzing the aminosilane, the hydrolyzed aminosilane is mixed with a silica dispersion and heated for the first time to obtain aminated silica. The aminated silica, propanesulfonate lactone, and the first solvent are mixed and heated a second time to obtain zwitterionic modified silica nanospheres. The zwitterionic modified nano silica spheres, silica sol, titanium dioxide, crosslinking agent, photoinitiator, and second solvent are mixed to obtain the organic-inorganic hybrid wear-resistant and anti-fog coating. The crosslinking agent is pentaerythritol triacrylate.

2. The production method according to claim 1, wherein The lifting speed of the dip-lifting method is 10~200mm / min; The UV curing wavelength is 365nm, the illumination intensity is 180~210mW / cm 2 , the illumination time is 1~3h, and the illumination temperature is room temperature.

3. The production method according to claim 1, wherein The hydrolysis process includes: mixing the aminosilane, water, and ethanol, and then hydrolyzing it under acidic conditions; The aminosilane includes one or more of N-aminoethyl-γ-aminopropyltrimethoxysilane, N,N-dimethyl-3-aminopropyltrimethoxysilane, N,N-diethyl-3-(trimethoxysilyl)propylamine, phenylaminomethyltriethoxysilane and γ-aminopropyltriethoxysilane. The mass ratio of aminosilane, water and ethanol is (10~40):(2~15):(50~100). The pH value of the acidic conditions is 2 to 6; the acid solution providing the acidic conditions is one or more of acetic acid, nitric acid, and hydrochloric acid, and the mass percentage concentration of the acid solution is 30% to 40%. The hydrolysis temperature is 15~25℃ and the time is 1~5h.

4. The production method according to claim 1, wherein The silica dispersion comprises silica nanoparticles and an aqueous ethanol solution; The mass ratio of the silica nanoparticles to the ethanol aqueous solution is 1:(10~40). The volume ratio of ethanol to water in the ethanol-water solution is (1~5):1; The mass ratio of the hydrolyzed aminosilane to the silica nanoparticles is (1~4):1; The first heating temperature is 60℃, and the time is 4~8h.

5. The production method according to claim 1, wherein The mass ratio of the aminated silica to propanesulfonate lactone is (1~3):1; The total mass ratio of the aminated silica and propanesulfonate lactone to the first solvent is 1:(2~5). The first solvent includes one or more of acetone, acetonitrile, toluene, diethyl ether, and methanol; The second heating temperature is 80℃, and the time is 4~8h.

6. The production method according to claim 1, wherein The method for preparing the silica sol includes: mixing tetraethyl orthosilicate, alcohol, water and inorganic acid, and then hydrolyzing and aging them sequentially to obtain the silica sol; The volume ratio of the tetraethyl orthosilicate, alcohol, water, and inorganic acid is (1~5):(12~20):(0.5~1.5):0.1; The alcohols include ethanol and / or propanol; The inorganic acid has a mass percentage concentration of 20-40%, and the inorganic acid is nitric acid or hydrochloric acid; The hydrolysis temperature is 20~25℃; the time is 1~6h; The static aging process is carried out at room temperature for 1 to 3 days. The mass ratio of the zwitterion-modified nanosilica spheres to the silica sol is 100: (1-10).

7. The production method according to claim 1 or 6, wherein The mass ratio of the zwitterion-modified nanosilica spheres to the crosslinking agent is (10-100):

1. The photoinitiator comprises one or more of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-methylphenylpropane-1-ketone, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, and benzophenone. The mass ratio of the zwitterion-modified nanosilica spheres to the photoinitiator is (50-200):

1. The titanium dioxide is nanometer titanium dioxide colloid, and the mass ratio of the nanometer titanium dioxide colloid to the silica sol is (1-3):

1. The second solvent comprises ethanol and water in a mass ratio of 1: (1-5).

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