Self-lubricating wear-resistant anti-fog coating and preparation method and application thereof

Abstract

The present application relates to the technical field of material surface modification, and particularly relates to a self-lubricating wear-resistant anti-fog coating and a preparation method and application thereof.The present application provides a self-lubricating wear-resistant anti-fog coating, which comprises an inorganic adhesive layer and an organic anti-fog coating layer arranged in sequence on the surface of a substrate; the preparation raw material of the inorganic adhesive layer is a vinyl silicon sol mixed coating material; the preparation raw material of the vinyl silicon sol mixed coating material comprises tetraethyl orthosilicate, a vinyl silane coupling agent, a first alcohol, water and an inorganic acid; the preparation raw material of the organic anti-fog coating layer is an anti-fog coating material, and the preparation raw material of the anti-fog coating material comprises a hydrophilic polymer, a monovinyl-terminated polydimethylsiloxane, a crosslinking agent, a photoinitiator and a second alcohol.The self-lubricating wear-resistant anti-fog coating has high interfacial bonding strength and excellent anti-fog performance, and the substrate applied is not limited.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of material surface modification, in particular to a self-lubricating wear-resistant anti-fog coating and a preparation method and application thereof. BACKGROUND

[0002] Transparent materials play an important role in the fields of aerospace, military equipment, medical devices and optoelectronic devices due to their excellent optical properties. However, when temperature difference changes in the environment, water vapor in the air is easily condensed into water droplets on the surface of the transparent material, producing fog, which affects the light transmittance and visibility of the transparent material. For example, fog on the windshield of a car affects the driver's field of vision, and fog on the endoscope during surgery is not conducive to the safe performance of the surgery. At present, the main ideas to solve the problem of fogging on the surface of transparent optical materials are divided into two categories: controlling the environmental parameters of the solid-liquid interface and surface modification. The former method is to accelerate the evaporation of fog droplets by heating or increasing air flow, such as the defogging and defrosting system of the front windshield of a car. However, this method is costly and has limited application environment. The latter method is usually to change the wetting properties of the substrate by coating a hydrophilic coating. The coating absorbs water molecules through hydrophilic groups and reduces the surface tension of water, which reduces the contact angle of water droplets on the substrate surface. The fog droplets on the substrate surface can quickly spread out, forming a uniform layer of water ink and no longer scattering the incident light, thereby achieving the effect of anti-fogging.

[0003] Coating a hydrophilic polymer on the surface can effectively enhance the interfacial hydrophilicity and give the surface excellent anti-fogging effect. However, the hydrophilic polymer has poor stability, and the coating is easy to swell and fall off in a humid environment, and is easy to be abraded and lose transparency when subjected to external force. SUMMARY

[0004] Therefore, the present application aims to provide a self-lubricating wear-resistant anti-fog coating and a preparation method and application thereof. The self-lubricating wear-resistant anti-fog coating has high interfacial bonding strength and excellent anti-fogging performance, and the application of the substrate is not limited.

[0005] In order to achieve the above-mentioned application purpose, the present application provides the following technical solutions:

[0006] The present application provides a self-lubricating wear-resistant anti-fog coating, which comprises an inorganic bonding layer and an organic anti-fog coating layer arranged in sequence on the surface of a substrate.

[0007] The preparation raw material of the inorganic bonding layer is a vinyl silicone sol mixed coating material; the preparation raw material of the vinyl silicone sol mixed coating material comprises tetraethyl orthosilicate, a vinyl silane coupling agent, a first alcohol, water and an inorganic acid.

[0008] The raw material for preparing the organic anti-fog coating is an anti-fog coating, and the raw material for preparing the anti-fog coating comprises a hydrophilic polymer, a monovinyl-terminated polydimethylsiloxane, a crosslinking agent, a photoinitiator and a second alcohol.

[0009] Preferably, the volume ratio of the first alcohol, tetraethyl orthosilicate, water and inorganic acid is (12-20):(1-5):(0.5-1.5):0.2.

[0010] The mass ratio of the tetraethyl orthosilicate and the vinyl silane coupling agent is (20-150):1.

[0011] Preferably, the first alcohol comprises ethanol or isopropanol.

[0012] The inorganic acid comprises nitric acid or hydrochloric acid.

[0013] The vinyl silane coupling agent comprises one or more of methyltrivinylsilane, dimethyldivinylsilane, γ-methacryloyloxypropyltrimethoxysilane and vinyltris(β-methoxyethoxy)silane.

[0014] Preferably, the preparation method of the vinyl silicate sol mixed coating comprises the following steps:

[0015] After mixing the tetraethyl orthosilicate, the vinyl silane coupling agent, the first alcohol, the water and the inorganic acid, hydrolysis and standing and aging are sequentially performed to obtain the vinyl silicate sol mixed coating.

[0016] The hydrophilic polymer comprises one or more of polymethacrylic acid, polyvinylpyrrolidone, polyethyleneimine and polyethylene glycol.

[0017] The crosslinking agent comprises one or more of polyethylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate and pentaerythritol hexaacrylate.

[0018] The photoinitiator comprises one or more of benzophenone, 2-hydroxy-2-methyl-1-phenylpropanone and 1-hydroxycyclohexyl phenyl ketone.

[0019] The second alcohol comprises ethanol or isopropanol.

[0020] Preferably, the mass ratio of the hydrophilic polymer, the monovinyl-terminated polydimethylsiloxane, the crosslinking agent, the photoinitiator and the second alcohol is (20-50):(1-10):(1-5):(0.1-0.5):(100-200).

[0021] Preferably, the preparation method of the anti-fog coating comprises the following steps:

[0022] The hydrophilic polymer, monovinyl terminated polydimethylsiloxane, crosslinking agent, photoinitiator and second alcohol are mixed to obtain the anti-fog coating.

[0023] The application further provides a preparation method of the self-lubricating wear-resistant anti-fog coating.

[0024] After the first coating of the vinyl silicon sol mixture coating on the surface of the substrate, curing is performed to obtain the inorganic adhesive layer.

[0025] After the second coating of the anti-fog coating on the surface of the inorganic adhesive layer, UV curing is performed to obtain the self-lubricating wear-resistant anti-fog coating.

[0026] Preferably, the first coating is performed by dip coating, and the dip coating has a pulling speed of 10-200 mm / min.

[0027] The curing is performed by baking, and the baking has a temperature of 60-150 DEG C and a time of 0.5-6 h.

[0028] The second coating is performed by spin coating, and the spin coating comprises first spin coating and second spin coating performed in sequence; the first spin coating has a rotation speed of 200-500 rpm and a time of 5 s; and the second spin coating has a rotation speed of 1500-3000 rpm and a time of 20 s.

[0029] The application further provides an application of the self-lubricating wear-resistant anti-fog coating or the self-lubricating wear-resistant anti-fog coating prepared by the preparation method in the field of anti-fogging on the surface of an optical transparent member.

[0030] The application provides a self-lubricating wear-resistant anti-fog coating, which comprises an inorganic adhesive layer and an organic anti-fog coating arranged in sequence on the surface of a substrate; the preparation raw material of the inorganic adhesive layer is a vinyl silicon sol mixture coating; the preparation raw material of the vinyl silicon sol mixture coating comprises tetraethyl orthosilicate, a vinyl silane coupling agent, a first alcohol, water and an inorganic acid; and the preparation raw material of the organic anti-fog coating is an anti-fog coating; the preparation raw material of the anti-fog coating comprises a hydrophilic polymer, monovinyl terminated polydimethylsiloxane, a crosslinking agent, a photoinitiator and a second alcohol. The self-lubricating wear-resistant anti-fog coating has a double-layer composite structure, the upper layer is the organic anti-fog coating, the lower layer is the inorganic adhesive layer, and the layers are connected by covalent bonds, so that the bonding strength of the organic anti-fog coating and the substrate is improved; the organic anti-fog coating is a hydrophilic-hydrophobic interpenetrating network (a hydrophilic polymer and a hydrophobic polymer (monovinyl terminated polydimethylsiloxane)), the hydrophilic polymer network controls the surface wettability, the anti-fog performance of the coating is given, the hydrophobic polymer has the functions of reducing the interfacial friction interaction and improving the anti-swelling capacity, and the components of the inorganic adhesive bottom layer are chemically combined to build the adhesion strength and improve the wear resistance of the coating.

[0031] The application further provides a preparation method of the self-lubricating wear-resistant anti-fog coating, comprising the following steps: coating the vinyl silicon sol mixed coating on the surface of the substrate, and then performing solidification to obtain an inorganic adhesive layer; coating the anti-fog coating on the surface of the inorganic adhesive layer, and then performing UV solidification to obtain the self-lubricating wear-resistant anti-fog coating. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 The transmittance curves of the glass pieces cleaned, the glass pieces modified with the pure hydrophilic polymer layer according to Comparative Example 1 and the glass pieces modified with the self-lubricating wear-resistant anti-fog coating according to Example 1;

[0033] Figure 2 The anti-fog performance photographs of the glass pieces modified with the self-lubricating wear-resistant anti-fog coating prepared in Example 1 and the blank glass pieces;

[0034] Figure 3 The friction coefficient curves of the glass pieces modified with the pure hydrophilic polymer layer according to Comparative Example 1 and the glass pieces modified with the self-lubricating wear-resistant anti-fog coating according to Example 1;

[0035] Figure 4 The microscope photographs of the glass pieces modified with the pure hydrophilic polymer layer according to Comparative Example 1 and the glass pieces modified with the self-lubricating wear-resistant anti-fog coating according to Example 1 after 50 times of friction experiments.

[0036] Figure 5 The microscope photographs and the anti-fog performance photographs of the glass pieces modified with the self-lubricating wear-resistant anti-fog coating prepared in Examples 2-5 after 50 times of friction experiments. DETAILED DESCRIPTION

[0037] The application provides a self-lubricating wear-resistant anti-fog coating, which comprises an inorganic adhesive layer and an organic anti-fog coating arranged in sequence on the surface of a substrate.

[0038] The preparation raw material of the inorganic adhesive layer is a vinyl silicon sol mixed coating; and the preparation raw material of the vinyl silicon sol mixed coating comprises tetraethyl orthosilicate, a vinyl silane coupling agent, a first alcohol, water and an inorganic acid.

[0039] The preparation raw material of the organic anti-fog coating is an anti-fog coating; and the preparation raw material of the anti-fog coating comprises a hydrophilic polymer, a monovinyl-terminated polydimethylsiloxane (PDMS-MA), a crosslinking agent, a photoinitiator and a second alcohol.

[0040] In the present application, all the preparation raw materials are commercially available products well known to those skilled in the art, unless otherwise specified.

[0041] The material of the substrate is not particularly limited in the present application, and any material well known to those skilled in the art can be used.

[0042] In the present application, the thickness of the inorganic adhesive layer is preferably 50-200 nm, and more preferably 70-150 nm. In the specific embodiments of the present application, the thickness of the inorganic adhesive layer can be 70 nm, 100 nm, 150 nm, 80 nm or 120 nm.

[0043] In the present application, the preparation raw material of the inorganic adhesive layer is preferably a vinyl silicone sol mixed coating material; and the preparation raw material of the vinyl silicone sol mixed coating material preferably comprises tetraethyl orthosilicate, a vinyl silane coupling agent, a first alcohol, water and an inorganic acid.

[0044] In the present application, the volume ratio of the first alcohol, tetraethyl orthosilicate, water and inorganic acid is preferably (12-20):(1-5):(0.5-1.5):0.2, and more preferably (14-18):(2-3):(0.8-1.2):0.2. In the embodiments of the present application, the volume ratio of the first alcohol, tetraethyl orthosilicate, water and inorganic acid can be 12:2:1:0.2.

[0045] In the present application, the mass ratio of the tetraethyl orthosilicate and the vinyl silane coupling agent is preferably (20-150):1, and more preferably (60-120):1. In the embodiments of the present application, the mass ratio of the tetraethyl orthosilicate and the vinyl silane coupling agent can be 40:1.

[0046] In the present application, the first alcohol preferably comprises ethanol or isopropanol. In the embodiments of the present application, the first alcohol can be ethanol.

[0047] In the present application, the mass percentage concentration of the inorganic acid is preferably 30-80%, and more preferably 30-70%; and the inorganic acid preferably comprises nitric acid or hydrochloric acid, the mass percentage concentration of the nitric acid is preferably 68%, and the mass percentage concentration of the hydrochloric acid is preferably 36%. In the embodiments of the present application, the inorganic acid can be nitric acid with a mass percentage concentration of 68%.

[0048] In the present application, the vinyl silane coupling agent preferably includes one or several of methyltrivinylsilane, dimethyldivinylsilane (DDS), γ-methacryloxypropyltrimethoxysilane (KH570), and vinyltris(β-methoxyethoxy)silane (A-172), and the present application does not have any special limitation on the ratio of the above-mentioned specific substances when the vinyl silane coupling agent is two or more of the above-mentioned specific choices, and the mixing can be performed in any ratio. In the embodiments of the present application, the vinyl silane coupling agent can be DDS, KH570, or A-172.

[0049] In the present application, the preparation method of the vinyl silicate sol mixed coating includes the following steps:

[0050] After the tetraethyl orthosilicate, the vinyl silane coupling agent, the first alcohol, water, and the inorganic acid are mixed, the hydrolysis and the standing aging are sequentially performed to obtain the vinyl silicate sol mixed coating.

[0051] In the present application, the mixing is preferably performed under stirring, and the present application does not have any special limitation on the process of the stirring, which can be performed by using the process well known to those skilled in the art. In the embodiments of the present application, the mixing can be that the first alcohol, the tetraethyl orthosilicate, water, and the inorganic acid are uniformly mixed under stirring, and then the vinyl silane coupling agent is added.

[0052] In the present application, the temperature of the hydrolysis is preferably 20-30°C, more preferably 23-27°C, and the time is preferably 1-6h, 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, which can be performed 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.

[0053] In the present application, the temperature of the standing aging is preferably 20-30°C, and the time is preferably 1-7 days, more preferably 3-5 days. In the embodiments of the present application, the temperature of the standing aging can be 25°C, and the time can be 3 days or 5 days.

[0054] In the present application, the thickness of the organic anti-fog coating is preferably 50-150μm, more preferably 100μm.

[0055] In the present application, the hydrophilic polymer preferably includes one or more of poly(methacrylic acid) (PAA), poly(vinylpyrrolidone) (PVP), poly(ethyleneimine) (PEI), and poly(ethylene glycol) (PEG). When the hydrophilic polymer is two or more of the above specific choices, the present application does not have any particular limitation on the ratio of the above specific substances, and mixing in any ratio is possible. In an embodiment of the present application, the hydrophilic polymer can be PVP, PEG, PEI, or PEI and PVP in a mass ratio of 2:3.

[0056] In the present application, the crosslinking agent includes one or more of poly(ethylene glycol) diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, and pentaerythritol hexaacrylate. When the crosslinking agent is two or more of the above specific choices, the present application does not have any particular limitation on the ratio of the above specific substances, and mixing in any ratio is possible. In an embodiment of the present application, the crosslinking agent can be pentaerythritol triacrylate.

[0057] In the present application, the photoinitiator preferably includes one or more of benzophenone (Bp), 2-hydroxy-2-methyl-1-phenylpropanone, and 1-hydroxycyclohexyl phenyl ketone (UV-184). When the photoinitiator is two or more of the above specific choices, the present application does not have any particular limitation on the ratio of the above specific substances, and mixing in any ratio is possible. In an embodiment of the present application, the photoinitiator can be UV-184 or Bp.

[0058] In the present application, the second alcohol preferably includes ethanol or isopropanol. In an embodiment of the present application, the second alcohol can be ethanol.

[0059] In the present application, the mass ratio of the hydrophilic polymer, the monovinyl-terminated polydimethylsiloxane, the crosslinking agent, the photoinitiator, and the second alcohol is preferably (20-50):(1-10):(1-5):(0.1-0.5):(100-200), and more preferably (30-40):(3-7):(3-5):(0.2-0.3):(150-200). In an embodiment of the present application, the mass ratio of the hydrophilic polymer, the monovinyl-terminated polydimethylsiloxane, the crosslinking agent, the photoinitiator, and the second alcohol can be 30:7:3:0.2:150, 40:3:4:0.2:180, 40:4:4:0.2:200, 30:3:3:0.2:200, or 50:5:5:0.3:200.

[0060] In the present application, the method of preparing the anti-fog coating preferably includes the following steps:

[0061] The hydrophilic polymer, monovinyl-terminated polydimethylsiloxane, crosslinking agent, photoinitiator and second alcohol are mixed to obtain the anti-fog coating.

[0062] In the present application, the mixing is preferably carried out at room temperature, in the dark and under stirring, the stirring time is preferably 6-24h, more preferably 12h; the present application does not have any special limitation on the stirring speed, which is carried out by using the speed well known to those skilled in the art, and ensuring uniform mixing within the above-mentioned stirring time.

[0063] The present application also provides a preparation method of the self-lubricating wear-resistant anti-fog coating as described in the above technical solution, comprising the following steps:

[0064] After the first coating of the vinyl silicone sol mixed coating on the surface of the substrate, curing is carried out to obtain an inorganic bonding layer.

[0065] After the second coating of the anti-fog coating on the surface of the inorganic bonding layer, UV curing is carried out to obtain the self-lubricating wear-resistant anti-fog coating.

[0066] The present application carries out curing after the first coating of the vinyl silicone sol mixed coating on the surface of the substrate to obtain an inorganic bonding layer.

[0067] In the present application, the first coating method is preferably dip coating, and the pulling speed of the dip coating is preferably 10-200mm / min, more preferably 20-100mm / min. In the embodiments of the present application, the pulling speed of the dip coating can be 20mm / min, 50mm / min, 100mm / min, 30mm / min or 60mm / min.

[0068] In the present application, the curing method is preferably baking; the baking temperature is preferably 60-150℃, more preferably 80-120℃; the baking time is preferably 0.5-6h, more preferably 0.5-2h. In the embodiments of the present application, the baking temperature can be 80℃ or 120℃, and the time can be 1h or 0.5h.

[0069] After obtaining the inorganic bonding layer, the present application carries out UV curing after the second coating of the anti-fog coating on the surface of the inorganic bonding layer to obtain the self-lubricating wear-resistant anti-fog coating.

[0070] In the present application, the second coating method is preferably spin coating, which preferably comprises a first spin coating and a second spin coating performed in sequence, the first spin coating preferably has a rotation speed of 200-500 rpm, more preferably 300-400 rpm, and a time of 5 s; the second spin coating preferably has a rotation speed of 1500-3000 rpm, more preferably 2000-2500 rpm, and a time of 20 s. In the embodiments of the present application, the first spin coating can have a rotation speed of 300 rpm and a time of 5 s; the second spin coating can have a rotation speed of 2000 rpm and a time of 20 s.

[0071] In the present application, the UV curing temperature is preferably room temperature, the UV curing light wavelength is preferably 365 nm, the light intensity is preferably 180-250 mW / cm 2 , more preferably 190-200 mW / cm 2 , and the time is preferably 0.5-3 h, more preferably 1-2 h. In the embodiments of the present application, the UV curing light wavelength can be 365 nm, the light intensity can be 250 mW / cm 2 , and the time can be 2 h.

[0072] The present application also provides the use of the self-lubricating wear-resistant anti-fog coating prepared by the above-mentioned technical solution or the preparation method in the field of anti-fogging on the surface of optical transparent members. The present application does not have any special limitation on the method of use, which can be carried out by using methods well known to those skilled in the art.

[0073] 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 a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0074] Embodiment 1

[0075] After 12 mL of ethanol, 2 mL of tetraethyl orthosilicate, 1 mL of water and 0.2 mL of 68% mass percentage nitric acid are uniformly mixed under stirring, 0.05 mL of KH570 is added, and stirring is continued for 1 h, and aging is carried out for 3 days to obtain a vinyl silicone sol mixed coating;

[0076] 30 g of PVP, 7 g of PDMS-MA, 3 g of pentaerythritol triacrylate, 0.2 g of UV-184 and 150 g of ethanol are mixed and stirred in the dark until a transparent and uniform solution is obtained to obtain an anti-fog coating;

[0077] The clean glass sheet was immersed in the vinyl-silica sol mixed coating solution, and then pulled out by a pulling machine at a speed of 20 mm / min. The inorganic adhesive layer (70 nm in thickness) was obtained after baking at 80°C for 1 h.

[0078] The anti-fog coating was spin-coated on the surface of the inorganic adhesive layer (first at a speed of 300 rpm for 5 s, and then at a speed of 2000 rpm for 20 s), and then cured under UV light at 365 nm for 2 h (the light intensity was 250 mW / cm 2 ). Thus, a glass sheet modified with a self-lubricating wear-resistant anti-fog coating layer (the thickness of the organic anti-fog coating layer was 100 μm) was prepared.

[0079] Comparative Example 1

[0080] 30 g of PVP, 3 g of pentaerythritol triacrylate, 0.2 g of UV-184 and 150 g of ethanol were mixed to form a transparent and uniform solution under dark conditions. Thus, a comparative anti-fog coating was prepared.

[0081] The comparative anti-fog coating was spin-coated on the surface of a clean glass sheet (first at a speed of 300 rpm for 5 s, and then at a speed of 2000 rpm for 20 s), and then cured under UV light at 365 nm for 2 h (the light intensity was 250 mW / cm 2 ). Thus, a glass sheet modified with a pure hydrophilic polymer layer was prepared.

[0082] Test Example 1

[0083] The transmittance of a clean glass sheet, the glass sheet modified with a pure hydrophilic polymer layer according to Comparative Example 1 and the glass sheet modified with a self-lubricating wear-resistant anti-fog coating layer according to Example 1 was tested by a UV-visible spectrophotometer. The test results are shown in Figure 1 It can be seen from Figure 1 that the transmittance curves of the clean glass sheet, the glass sheet modified with a pure hydrophilic polymer layer according to Comparative Example 1 and the glass sheet modified with a self-lubricating wear-resistant anti-fog coating layer according to Example 1 are similar, which indicates that the coating layer has little effect on the light transmittance of the glass.

[0084] The glass sheet modified with a self-lubricating wear-resistant anti-fog coating layer according to Example 1 was placed in a water bath at 60°C, about 10 cm away from the liquid surface, and left for different time. The anti-fog performance of the surface was tested with a blank glass sheet as a control sample. The test results are shown in Figure 2 It can be seen from Figure 2 that no obvious fog droplets appeared on the surface of the wear-resistant anti-fog coating layer after 12 hours of anti-fog testing, which indicates that the coating layer has excellent anti-fog performance.

[0085] The glass sheet modified with the pure hydrophilic polymer layer described in Comparative Example 1 and the glass sheet modified with the self-lubricating wear-resistant anti-fog coating described in Example 1 were respectively placed in air to be abraded against a piece of cloth under the condition of a 2N load and a 1Hz frequency, wherein Figure 3 It can be seen from the friction coefficient curves of the glass sheet modified with the pure hydrophilic polymer layer described in Comparative Example 1 and the glass sheet modified with the self-lubricating wear-resistant anti-fog coating described in Example 1 that the friction coefficient of the coating surface of Example 1 can still be maintained at about 0.05 within 10,000 cycles, compared with the high friction coefficient (0.25) of the glass sheet modified with the pure water polymer layer described in Comparative Example 1, and the self-lubricating wear-resistant anti-fog coating has good self-lubricating wear-resistant properties; Figure 3

[0086] The glass sheet modified with the pure hydrophilic polymer layer described in Comparative Example 1 and the glass sheet modified with the self-lubricating wear-resistant anti-fog coating described in Example 1 were placed under an optical microscope to observe the surface morphology after 50 times of friction experiments, wherein Figure 4 It can be seen from the microscope images of the glass sheet modified with the pure hydrophilic polymer layer described in Comparative Example 1 and the glass sheet modified with the self-lubricating wear-resistant anti-fog coating described in Example 1 after 50 times of friction experiments that obvious and large abrasions appeared on the surface of the pure hydrophilic polymer layer in the glass sheet modified with the pure hydrophilic polymer layer described in Comparative Example 1; compared therewith, no obvious abrasions were observed on the surface of the self-lubricating wear-resistant anti-fog coating in the glass sheet modified with the self-lubricating wear-resistant anti-fog coating described in Example 1, indicating that the self-lubricating wear-resistant anti-fog coating has good wear resistance. Figure 4

[0087] Example 2

[0088] After 12mL of ethanol, 2mL of ethyl silicate, 1mL of water and 0.2mL of nitric acid with a concentration of 68% were uniformly mixed under stirring, 0.05mL of DDS was added, and the stirring was continued for 1h, and the mixture was left to stand for 5 days to obtain a vinyl silicon sol mixed coating material;

[0089] 40g of PVP, 3g of PDMS-MA, 4g of pentaerythritol triacrylate, 0.2g of UV-184 and 180g of ethanol were mixed and stirred in the dark until a transparent and uniform solution was obtained to obtain an anti-fog coating material;

[0090] A clean glass sheet was immersed in the vinyl silicon sol mixed coating material, and then pulled out by a pulling machine at a speed of 50mm / min, and baked at 120°C for 0.5h to obtain an inorganic bonding layer (with a thickness of 100nm);

[0091] ​​The anti-fog coating was spin-coated on the surface of the inorganic adhesive layer (first spin-coated at a speed of 300 rpm for 5 s, and then spin-coated at a speed of 2000 rpm for 20 s), and then cured under UV light at 365 nm for 2 h (the light intensity was 250 mW / cm 2 ), to obtain a glass sheet modified with a self-lubricating wear-resistant anti-fog coating (the thickness of the organic anti-fog coating was about 98 μm).

[0092] After testing, the anti-fog performance, lubricating performance, and wear resistance of the glass sheet modified with the self-lubricating wear-resistant anti-fog coating were similar to those of Example 1. After 50 friction experiments, only slight scratches appeared on the surface of the coating, and the anti-fog performance of the coating was good Figure 5 .

[0093] Example 3

[0094] After 12 mL of ethanol, 2 mL of tetraethyl orthosilicate, 1 mL of water, and 0.2 mL of 68% concentrated nitric acid were uniformly mixed under stirring, 0.05 mL of A-172 was added, and stirring was continued for 1 h, and the mixture was aged for 3 days, to obtain a vinyl silicone sol mixed coating;

[0095] 40 g of PEG, 4 g of PDMS-MA, 4 g of pentaerythritol triacrylate, 0.2 g of UV-184, and 200 g of ethanol were mixed and stirred in the dark until a transparent and uniform solution was obtained, to obtain an anti-fog coating;

[0096] The cleaned glass sheet was immersed in the vinyl silicone sol mixed coating, and then pulled out by a pulling machine at a speed of 100 mm / min, and baked at 120°C for 0.5 h, to obtain an inorganic adhesive layer (the thickness was 150 nm);

[0097] The anti-fog coating was spin-coated on the surface of the inorganic adhesive layer (first spin-coated at a speed of 300 rpm for 5 s, and then spin-coated at a speed of 2000 rpm for 20 s), and then cured under UV light at 365 nm for 2 h (the light intensity was 250 mW / cm 2 ), to obtain a glass sheet modified with a self-lubricating wear-resistant anti-fog coating (the thickness of the organic anti-fog coating was about 95 μm).

[0098] After testing, the anti-fog performance, lubricating performance, and wear resistance of the glass sheet modified with the self-lubricating wear-resistant anti-fog coating were similar to those of Example 1. After 50 friction experiments, only slight scratches appeared on the surface of the coating, and the anti-fog performance of the coating was good Figure 5 .

[0099] Example 4

[0100] After 12 mL of ethanol, 2 mL of tetraethyl orthosilicate, 1 mL of water and 0.2 mL of nitric acid with a concentration of 68% are mixed uniformly under stirring, 0.05 mL of KH570 is added, stirring is continued for 1 h, and standing and aging is performed for 5 days to obtain a vinyl silicone sol mixed coating;

[0101] 30 g of PEI, 3 g of PDMS-MA, 3 g of pentaerythritol triacrylate, 0.2 g of Bp and 200 g of ethanol are mixed and stirred in the dark until a transparent and uniform solution is obtained to obtain an anti-fog coating;

[0102] A clean glass sheet is immersed in the vinyl silicone sol mixed coating, then pulled out by a pulling machine at a speed of 30 mm / min, and baked at 80°C for 0.5 h to obtain an inorganic bonding layer (thickness of 80 nm);

[0103] After the anti-fog coating is spin-coated on the surface of the inorganic bonding layer (spin-coated at a speed of 300 rpm for 5 s and then at a speed of 2000 rpm for 20 s), it is cured under 365 nm UV light for 2 h (light intensity of 250 mW / cm 2 ), to obtain a glass sheet modified with a self-lubricating wear-resistant anti-fog coating (thickness of the organic anti-fog coating is about 90 μm).

[0104] After testing, the anti-fog performance, lubricating performance and wear resistance of the glass sheet modified with the self-lubricating wear-resistant anti-fog coating are similar to those of Example 1. After 50 times of rubbing experiments, only a shallow scratch appears on the surface of the coating, and the anti-fog performance of the coating is good Figure 5 ).

[0105] Example 5

[0106] After 12 mL of ethanol, 2 mL of tetraethyl orthosilicate, 1 mL of water and 0.2 mL of nitric acid with a concentration of 68% are mixed uniformly under stirring, 0.05 mL of KH570 is added, stirring is continued for 1 h, and standing and aging is performed for 5 days to obtain a vinyl silicone sol mixed coating;

[0107] 20 g of PEI, 30 g of PVP, 5 g of PDMS-MA, 5 g of pentaerythritol triacrylate, 0.3 g of Bp and 200 g of ethanol are mixed and stirred in the dark until a transparent and uniform solution is obtained to obtain an anti-fog coating;

[0108] A clean glass sheet is immersed in the vinyl silicone sol mixed coating, then pulled out by a pulling machine at a speed of 30 mm / min, and baked at 80°C for 0.5 h to obtain an inorganic bonding layer (thickness of 80 nm);

[0109] After spin-coating the anti-fog coating on the surface of the inorganic bonding layer (spin-coating at a speed of 300 rpm for 5 s and then at a speed of 2000 rpm for 20 s), the glass sheet modified with the self-lubricating wear-resistant anti-fog coating was prepared by curing under UV light at 365 nm for 2 h (the light intensity was 250 mW / cm 2 ).

[0110] The anti-fog performance, lubricating performance and wear resistance of the glass sheet modified with the self-lubricating wear-resistant anti-fog coating were similar to those of Example 1. After 50 times of friction test, only slight scratches were observed on the surface of the coating, and the anti-fog performance of the coating was good Figure 5 .

[0111] The above description is only preferred embodiments of the present application, and does not limit the present application in any form. It should be noted that, for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should be considered as the protection scope of the present application.

Claims

1. A self-lubricating wear-resistant anti-fog coating, characterized in that, The inorganic adhesive layer and the organic anti-fog coating layer are sequentially arranged on the surface of the substrate; The preparation raw material of the inorganic adhesive layer is a vinyl silicone sol mixed coating; the preparation raw material of the vinyl silicone sol mixed coating includes tetraethyl orthosilicate, a vinyl silane coupling agent, a first alcohol, water and an inorganic acid; The preparation raw material of the organic anti-fog coating layer is an anti-fog coating; the preparation raw material of the anti-fog coating includes a hydrophilic polymer, a monovinyl-terminated polydimethylsiloxane, a crosslinking agent, a photoinitiator and a second alcohol; The hydrophilic polymer is polyvinylpyrrolidone; After the first coating of the vinyl silicone sol mixed coating on the surface of the substrate, curing is performed to obtain the inorganic adhesive layer; After the second coating of the anti-fog coating on the surface of the inorganic adhesive layer, UV curing is performed to obtain the self-lubricating wear-resistant anti-fog coating.

2. The self-lubricating wear-resistant anti-fog coating of claim 1, wherein, The volume ratio of the first alcohol, tetraethyl orthosilicate, water and inorganic acid is (12-20):(1-5):(0.5-1.5):0.2; The mass ratio of the tetraethyl orthosilicate and the vinyl silane coupling agent is (20-150):

1.

3. The self-lubricating wear-resistant anti-fog coating according to claim 1 or 2, characterized in that, The first alcohol includes ethanol or isopropanol; The inorganic acid includes nitric acid or hydrochloric acid; The vinyl silane coupling agent includes one or more of methyltrivinylsilane, dimethyldivinylsilane, γ-methacryloyloxypropyltrimethoxysilane and vinyltris(β-methoxyethoxy)silane.

4. The self-lubricating, wear resistant, anti-fog coating of claim 3, wherein, The preparation method of the vinyl silicone sol mixed coating includes the following steps: After the mixing of the tetraethyl orthosilicate, the vinyl silane coupling agent, the first alcohol, the water and the inorganic acid, hydrolysis and standing and aging are sequentially performed to obtain the vinyl silicone sol mixed coating.

5. The self-lubricating, wear resistant, anti-fog coating of claim 1, wherein, The crosslinking agent includes one or more of polyethylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate and pentaerythritol hexaacrylate; The photoinitiator includes one or more of benzophenone, 2-hydroxy-2-methyl-1-phenylpropanone and 1-hydroxycyclohexyl phenyl ketone; The second alcohol includes ethanol or isopropanol.

6. The self-lubricating wear-resistant anti-fog coating according to claim 1 or 5, characterized in that, The mass ratio of the hydrophilic polymer, the monovinyl-terminated polydimethylsiloxane, the crosslinking agent, the photoinitiator and the second alcohol is (20-50):(1-10):(1-5):(0.1-0.5):(100-200).

7. The self-lubricating wear-resistant anti-fog coating of claim 6, wherein, The preparation method of the anti-fog coating includes the following steps: The hydrophilic polymer, the monovinyl-terminated polydimethylsiloxane, the crosslinking agent, the photoinitiator and the second alcohol are mixed to obtain the anti-fog coating.

8. The method of producing a self-lubricating wear-resistant anti-fog coating according to any one of claims 1 to 7, characterized in that, The preparation method includes the following steps: After the first coating of the vinyl silicone sol mixed coating on the surface of the substrate, curing is performed to obtain the inorganic adhesive layer; After the second coating of the anti-fog coating on the surface of the inorganic adhesive layer, UV curing is performed to obtain the self-lubricating wear-resistant anti-fog coating.

9. The production method according to claim 8, wherein The first coating is performed by dip coating, and the pulling speed of the dip coating is 10-200 mm / min; The curing is performed by baking, and the temperature of the baking is 60-150°C, and the time is 0.5-6 h; The second coating method is spin coating, and the spin coating comprises a first spin coating and a second spin coating performed in sequence; the first spin coating is performed at a rotation speed of 200-500 rpm for 5 s; and the second spin coating is performed at a rotation speed of 1500-3000 rpm for 20 s.

10. The self-lubricating wear-resistant anti-fog coating according to any one of claims 1-7 or prepared by the method according to claim 8 or 9 for use in the field of anti-fogging of optical transparent surfaces.

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