Dispersion-strengthened transparent wear-resistant amphiphobic coating and preparation method thereof

Abstract

The invention provides a dispersion-strengthened transparent wear-resistant amphiphobic coating and a preparation method thereof, and belongs to the technical field of functional protection materials. The preparation method comprises the following steps: mixing an organosilane compound, small molecular acid, water and an alcohol solvent, carrying out hydrolytic condensation reaction, and removing the solvent to obtain the low-surface-energy resin; uniformly mixing the low-surface-energy resin, a cross-linking agent, the epoxy modified SiO2 nanoparticles, a photoinitiator and an organic solvent to obtain a photocureable coating; the surface of a base material is coated with the photocureable coating, ultraviolet curing is carried out, and the dispersion-strengthened transparent wear-resistant amphiphobic coating is obtained. The dispersion-strengthened transparent wear-resistant amphiphobic coating provided by the invention has excellent wear resistance and light transmission.

Description

Technical Field

[0001] The present invention relates to the technical field of functional protective materials, and in particular to a dispersion-strengthened transparent wear-resistant amphiphobic coating and a preparation method thereof. Background Art

[0002] For optical materials and devices such as solar panels, optical lenses, safety goggles, electronic screens, and vehicle and building windows, coverage by contaminants can significantly impact performance, increase maintenance costs, and shorten service life.

[0003] In recent years, the study of surface wettability has garnered significant interest. A series of superwetting surfaces, inspired by the self-cleaning biomimetic concept of the lotus leaf, have been developed. These surfaces often achieve superhydrophobicity or even superoleophobicity by modulating the surface energy of the substrate. However, the construction of superwetting surfaces requires micro- and nanostructured surface textures, which are costly and easily damaged. Therefore, high-performance amphiphobic coatings are more suitable for practical applications.

[0004] Since the thickness, particles and roughness of the coating will affect the transmittance of light, the existing double-repellent coating has a general light transmittance and is difficult to be applied to optical components with strict requirements on light transmittance. In addition, optical components such as headlight covers and windshields that are susceptible to sandstorms also require protective coatings with excellent wear resistance. In order to improve wear resistance, hard particles (such as aluminum oxide, silicon carbide or silicon dioxide) are often added to the coating. These particles resist wear by enhancing the hardness of the coating or forming a wear-resistant network. However, the enhancement of the wear resistance of the coating is often accompanied by the loss of the light transmittance of the coating. Affected by the particle size and material compatibility, high concentrations of hard particles will still reduce the light transmittance due to interface reflection and multiple scattering, resulting in haze. Therefore, it is still a difficult challenge to achieve both high light transmittance and high wear resistance of double-repellent coatings at the same time. Summary of the Invention

[0005] In view of this, the object of the present invention is to provide a dispersion-strengthened transparent wear-resistant amphiphobic coating and a preparation method thereof. The dispersion-strengthened transparent wear-resistant amphiphobic coating provided by the present invention has both excellent wear resistance and light transmittance.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a method for preparing a dispersion-strengthened transparent wear-resistant amphiphobic coating, comprising the following steps:

[0008] Mixing an organic silane compound, a small molecule acid, water and an alcohol solvent, performing a hydrolysis condensation reaction, and removing the solvent to obtain a low surface energy resin; the organic silane compound includes an orthosilicate compound, a triethoxysilane compound, γ-glycidyloxypropyltriethoxysilane and triethoxysilylethyl mono-terminated polydimethylsiloxane;

[0009] The low surface energy resin, the crosslinking agent, the epoxy-modified SiO2 nanoparticles, the photoinitiator and the organic solvent are uniformly mixed to obtain a light-curing coating;

[0010] The light-curing coating is coated on the surface of a substrate and subjected to ultraviolet light curing to obtain a diffusion-strengthened, transparent, wear-resistant, and amphiphobic coating.

[0011] Preferably, the orthosilicate compound includes ethyl orthosilicate and / or butyl orthosilicate;

[0012] The triethoxysilane compound includes methyltriethoxysilane and / or phenyltriethoxysilane;

[0013] The mass ratio of the orthosilicate compound, the triethoxysilane compound, γ-glycidyloxypropyltriethoxysilane and triethoxysilylethyl mono-terminated polydimethylsiloxane is (3-12):(3-4):(3-12):(1-2).

[0014] Preferably, the small molecule acid includes one or more of hydrochloric acid, nitric acid and acetic acid;

[0015] The mass ratio of the organic silane compound to the small molecule acid is 20:1-3.

[0016] Preferably, the temperature of the hydrolysis condensation reaction is 60-80° C., and the time is 12-48 hours.

[0017] Preferably, the method for preparing the epoxy-modified SiO2 nanoparticles comprises the following steps:

[0018] The alcohol dispersion of SiO2 nanoparticles is mixed with epoxy silane, the pH value of the mixture is adjusted to acidic, and a modification reaction is carried out to obtain epoxy-modified SiO2 nanoparticles.

[0019] Preferably, the particle size of the SiO2 nanoparticles is 10 to 20 nm.

[0020] Preferably, the epoxy silane includes 3-glycidyloxypropyltriethoxysilane and / or 3-glycidyloxypropyltrimethoxysilane;

[0021] The mass ratio of the SiO2 nanoparticles to epoxy silane is 5 to 20:1.

[0022] Preferably, the cross-linking agent comprises one or more of pentaerythritol tetraacrylate, pentaerythritol hexaacrylate, octavinyl POSS and octaepoxycyclohexylhexyl-cage POSS;

[0023] The photoinitiator includes one or more of benzophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, diphenylformyl dimethylbenzyl ammonium salt and bis(4-tert-butylphenyl)iodine hexafluorophosphate.

[0024] Preferably, the mass ratio of the low surface energy resin to the epoxy-modified SiO2 nanoparticles is 10:0.05-0.2;

[0025] The mass ratio of the low surface energy resin to the crosslinking agent and the photoinitiator is 10:1-3:0.1-0.5;

[0026] The mass ratio of the low surface energy resin to the organic solvent is 10:5-10.

[0027] Preferably, the intensity of the UV curing is 100 to 500 mW / cm 2 , time is 1 to 10 minutes.

[0028] The present invention provides a dispersion-strengthened, transparent, wear-resistant, and amphiphobic coating prepared by the above-mentioned preparation method.

[0029] The present invention provides a method for preparing a dispersion-strengthened, transparent, and wear-resistant amphiphobic coating, characterized by comprising the following steps: mixing an organosilane compound, a small molecule acid, water, and an alcohol solvent, performing a hydrolysis-condensation reaction, and removing the solvent to obtain a low-surface-energy resin; uniformly mixing the low-surface-energy resin, a crosslinking agent, epoxy-modified SiO2 nanoparticles, a photoinitiator, and an organic solvent to obtain a photocurable coating; and coating the photocurable coating on a substrate surface and performing ultraviolet light curing to obtain a dispersion-strengthened, transparent, and wear-resistant amphiphobic coating. In the present invention, the epoxy-modified SiO2 nanoparticles serve as a dispersed phase, filling micro- and nano-scale structural defects in the coating and chemically bonding with the resin, thereby improving the mechanical strength and wear resistance of the coating. The freely extendable organosilicon polymer brushes in the coating impart self-lubricating and amphiphobic properties to the coating. Furthermore, the coating components exhibit good compatibility, and the nanoscale epoxy-modified silica particles can be incorporated into the coating network through epoxy self-crosslinking rather than being dispersed within the coating as fillers, thereby reducing light scattering. Therefore, the amphiphobic coating provided by the present invention exhibits high light transmittance.

[0030] At the same time, the preparation method provided by the present invention is easy to operate, the coating has good film-forming properties, and can be coated on the surface of most materials, which can meet the needs of practical applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is a graph showing the optical transmittance of the diffusion-enhanced transparent wear-resistant amphiphobic coating of Example 1;

[0032] Figure 2 This is an optical photograph of the diffusion-strengthened, transparent, wear-resistant amphiphobic coating of Example 1;

[0033] Figure 3 This is a water contact angle diagram of the dispersion-strengthened transparent wear-resistant amphiphobic coating of Example 1;

[0034] Figure 4 This is a graph showing the anti-fouling performance of the dispersion-strengthened transparent wear-resistant amphiphobic coating of Example 1;

[0035] Figure 5 This is a friction coefficient curve of the dispersion-strengthened transparent wear-resistant amphiphobic coating of Example 1;

[0036] Figure 6 Graph showing changes in contact angle and morphology of the dispersion-strengthened, transparent, wear-resistant, and amphiphobic coatings of Examples 1 to 5 after being rubbed with steel wool. DETAILED DESCRIPTION

[0037] The present invention provides a method for preparing a dispersion-strengthened transparent wear-resistant amphiphobic coating, comprising the following steps:

[0038] An organic silane compound, a small molecule acid, water and an alcohol solvent are mixed to undergo a hydrolysis condensation reaction, and a low surface energy resin is obtained after removing the solvent;

[0039] The low surface energy resin, the crosslinking agent, the epoxy-modified SiO2 nanoparticles, the photoinitiator and the organic solvent are uniformly mixed to obtain a light-curing coating;

[0040] The light-curing coating is coated on the surface of a substrate and subjected to ultraviolet light curing to obtain a diffusion-strengthened, transparent, wear-resistant, and amphiphobic coating.

[0041] Unless otherwise specified, the raw materials used in the present invention are all commercially available.

[0042] The present invention mixes an organosilane compound, a small molecule acid, water, and an alcohol solvent, performs a hydrolysis-condensation reaction, and removes the solvent to obtain a low-surface-energy resin. In the present invention, the organosilane compound includes an orthosilicate compound, a triethoxysilane compound, γ-glycidyloxypropyltriethoxysilane, and triethoxysilylethyl mono-terminated polydimethylsiloxane. In the present invention, the orthosilicate compound increases strength, the triethoxysilane compound increases toughness, the γ-glycidyloxypropyltriethoxysilane cures and crosslinks, and the triethoxysilylethyl mono-terminated polydimethylsiloxane provides self-lubrication. In the present invention, the mass ratio of the orthosilicate compound, the triethoxysilane compound, γ-glycidyloxypropyltriethoxysilane and triethoxysilylethyl mono-terminated polydimethylsiloxane is preferably (3-12):(3-4):(3-12):(1-2), and more preferably (5-10):(3-4):(5-10):(1-2).

[0043] In the present invention, the small molecule acid preferably includes one or more of hydrochloric acid, nitric acid, and acetic acid. In the present invention, the mass ratio of the organosilane compound to the small molecule acid is preferably 20:1 to 3, more preferably 20:2. In the present invention, the small molecule acid catalyzes hydrolysis and condensation.

[0044] In the present invention, the alcohol solvent is preferably ethanol. In the present invention, the mass ratio of the organosilane compound to water and the alcohol solvent is preferably 20:2-5:5-10, more preferably 20:3-4:6-8.

[0045] The present invention has no special requirements for the mixing method, and any mixing method known to those skilled in the art can be used, such as stirring. In the present invention, the temperature of the hydrolysis-condensation reaction is preferably 60 to 80° C., more preferably 70° C., and the time is preferably 12 to 48 hours, more preferably 24 hours.

[0046] In the present invention, the method of removing the solvent is preferably rotary evaporation. In the present invention, the contact angle of the low surface energy resin is preferably 95 to 110°.

[0047] After obtaining the low surface energy resin, the present invention uniformly mixes the low surface energy resin, a crosslinking agent, epoxy-modified SiO2 nanoparticles, a photoinitiator, and an organic solvent to obtain a light-cured coating. In the present invention, the method for preparing the epoxy-modified SiO2 nanoparticles preferably includes the following steps:

[0048] The alcohol dispersion of SiO2 nanoparticles is mixed with epoxy silane, the pH value of the mixture is adjusted to acidic, and a modification reaction is carried out to obtain epoxy-modified SiO2 nanoparticles.

[0049] In the present invention, the particle size of the SiO2 nanoparticles is preferably 10 to 20 nm, more preferably 15 nm. In the present invention, the alcohol solvent in the alcohol dispersion of the SiO2 nanoparticles is preferably ethanol, and the mass concentration of the SiO2 nanoparticles in the alcohol dispersion of the SiO2 nanoparticles is preferably 1 to 2%, more preferably 1 to 1.5%. In the present invention, the SiO2 nanoparticles and the alcohol solvent are preferably ultrasonically mixed to break up particle agglomerates to obtain the alcohol dispersion of the SiO2 nanoparticles. The ultrasonic power is preferably 250 W, and the time is preferably 30 minutes.

[0050] In the present invention, the epoxy silane preferably includes 3-glycidyloxypropyltriethoxysilane (GPTES) and / or 3-glycidyloxypropyltrimethoxysilane (KH560). In the present invention, the mass ratio of the SiO2 nanoparticles to the epoxy silane is preferably 5 to 20:1, more preferably 10:1.

[0051] After obtaining a mixture of SiO2 nanoparticles and epoxysilane, the present invention adjusts the pH of the mixture to an acidic level. In the present invention, the acidic pH is preferably 2 to 4, more preferably 3 to 4. In the present invention, the reagent for adjusting the pH is preferably acetic acid. Adjusting the pH to an acidic level is intended to catalyze the hydrolysis and condensation of the silane.

[0052] In the present invention, the temperature of the modification reaction is preferably room temperature, and the time is preferably 24 hours. After the modification reaction, the present invention preferably centrifuges and washes the obtained modification reaction solution, and the washing agent is preferably ethanol.

[0053] The mass ratio of the low surface energy resin to the epoxy-modified SiO2 nanoparticles of the present invention is preferably 10:0.05 to 0.2, more preferably 10:0.1 to 0.15. By controlling the mass ratio of the low surface energy resin to the epoxy-modified SiO2 nanoparticles, the present invention can enhance the mechanical strength of the coating while maintaining its transparency.

[0054] In the present invention, the cross-linking agent preferably includes one or more of pentaerythritol tetraacrylate, pentaerythritol hexaacrylate, octavinyl POSS and octaepoxycyclohexylhexyl-cage POSS; the present invention adopts the above-mentioned cross-linking agent, which has the characteristics of rapid reaction, high cross-linking degree, dense coating network, better bearing capacity, and can enhance the wear resistance of the coating.

[0055] In the present invention, the photoinitiator includes one or more of benzophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, diphenylformyl dimethylbenzyl ammonium salt and bis(4-tert-butylphenyl)iodine hexafluorophosphate; the organic solvent is preferably a polar organic solvent, more preferably one or more of ethanol, ethyl acetate, butyl acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate.

[0056] In the present invention, the mass ratio of the low surface energy resin to the crosslinking agent and the photoinitiator is preferably 10:1-3:0.1-0.5, more preferably 10:2:0.2-0.4. In the present invention, the mass ratio of the low surface energy resin to the organic solvent is preferably 10:5-10, more preferably 10:6-8.

[0057] In the present invention, the low surface energy resin, crosslinking agent, epoxy-modified SiO2 nanoparticles, photoinitiator and organic solvent are preferably mixed by stirring, more preferably by magnetic stirring; in the present invention, the mixing is preferably carried out under light-proof conditions.

[0058] After obtaining the light-curable coating, the present invention applies the light-curable coating to the surface of a substrate and performs ultraviolet light curing to obtain a diffusion-strengthened, transparent, wear-resistant, and amphiphobic coating. In the present invention, the substrate is preferably a transparent material, more preferably one or more of glass, polymethyl methacrylate, polycarbonate, and polyethylene terephthalate.

[0059] In the present invention, the coating method of the photocurable coating is preferably drop coating, and the coating thickness of the photocurable coating is preferably 50 to 150 μm, more preferably 80 to 120 μm, and further preferably 100 μm.

[0060] In the present invention, the wavelength of the ultraviolet light used for the ultraviolet curing is preferably 365 nm; the intensity of the ultraviolet curing is preferably 100 to 500 mW / cm 2 , more preferably 200 to 400 mW / cm 2 The time is preferably 1 to 10 minutes, more preferably 2 to 8 minutes, and even more preferably 5 minutes.

[0061] The present invention provides a dispersion-strengthened, transparent, wear-resistant, and amphiphobic coating prepared by the above-mentioned preparation method. In the present invention, the thickness of the dispersion-strengthened, transparent, wear-resistant, and amphiphobic coating is preferably 20 to 100 μm.

[0062] The dispersion-enhanced transparent wear-resistant amphiphobic coating and its preparation method provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0063] Example 1

[0064] The preparation method of the dispersion-strengthened transparent wear-resistant amphiphobic coating comprises the following steps:

[0065] (1) Synthesis of epoxy-modified SiO2 nanoparticles

[0066] 1 g of SiO2 nanoparticles with a particle size of 10-20 nm was dispersed in 99 g of anhydrous ethanol and ultrasonically treated for 30 min to break up the particle agglomerates to form a uniform dispersion. Subsequently, 0.1 g of KH560 and 0.1 g of water were added to the dispersion, and the pH value was adjusted to 4 with acetic acid. The mixture was stirred at room temperature for 24 h to fully react. The solvent was removed by centrifugation, and the mixture was washed three times with ethanol to obtain epoxy-modified SiO2 nanoparticles.

[0067] (2) Synthesis of low surface energy resin

[0068] Take 10g of ethyl orthosilicate, 5g of γ-glycidyloxypropyltriethoxysilane, 4g of methyltriethoxysilane, 1g of triethoxysilylethyl mono-terminated polydimethylsiloxane, 1g of acetic acid, 3g of water, and 5g of ethanol and add them to a 100mL round-bottom flask. After stirring at 70°C for 24h, the solvent is removed by rotary evaporation to obtain a low surface energy resin.

[0069] (3) Preparation of light-curing coatings

[0070] 10 g of low surface energy resin, 1 g of octavinyl POSS, 0.1 g of epoxy-modified SiO2 nanoparticles, 0.1 g of benzophenone, 0.1 g of diphenylformyl dimethylbenzyl ammonium salt, and 8 g of butyl acetate were mixed and magnetically stirred in the dark to obtain a light-curing coating.

[0071] (4) Preparation of dispersion-enhanced transparent wear-resistant amphiphilic coating

[0072] The prepared light-curing coating was dropped onto the glass surface, and naturally leveled. It was left at room temperature for 24 hours. After the solvent evaporated, the glass was placed under a UV lamp for 5 minutes with a light intensity of 250mW / cm 2 , with a wavelength of 365nm, a diffusion-enhanced, transparent, wear-resistant, and amphiphobic coating with a thickness of 50μm was obtained.

[0073] Example 2

[0074] The preparation method of the dispersion-strengthened transparent wear-resistant amphiphobic coating comprises the following steps:

[0075] (1) Synthesis of epoxy-modified SiO2 nanoparticles

[0076] 1 g of SiO2 nanoparticles with a particle size of 10 to 20 nm was dispersed in 99 g of anhydrous ethanol and ultrasonically treated for 30 minutes to break up the particle agglomerates to form a uniform dispersion. Subsequently, 0.1 g of GPTES and 0.1 g of water were added to the dispersion, and the pH was adjusted to 4 with acetic acid. The dispersion was stirred at room temperature for 24 hours to fully react. The solvent was removed by centrifugation, and the mixture was washed three times with ethanol to obtain epoxy-modified SiO2 nanoparticles.

[0077] (2) Synthesis of low surface energy resin

[0078] 5 g of ethyl orthosilicate, 10 g of γ-glycidyloxypropyltriethoxysilane, 4 g of methyltriethoxysilane, 1 g of triethoxysilylethyl mono-terminated polydimethylsiloxane, 1 g of acetic acid, 3 g of water, and 10 g of ethanol were added to a 100 mL round-bottom flask, stirred at 70 ° C for 24 h, and then the solvent was removed by rotary evaporation to obtain a low surface energy resin.

[0079] (3) Preparation of light-curing coatings

[0080] 10 g of low surface energy resin, 1 g of octaepoxycyclohexylhexyl-cage POSS, 0.05 g of epoxy-modified SiO2 nanoparticles, 0.1 g of bis(4-tert-butylphenyl)iodine hexafluorophosphate, and 8 g of propylene glycol methyl ether were mixed and magnetically stirred in the dark to obtain a light-curing coating.

[0081] (4) Preparation of dispersion-enhanced transparent wear-resistant amphiphilic coating

[0082] The prepared light-curing coating was dropped onto the glass surface, and naturally leveled. It was left at room temperature for 24 hours. After the solvent evaporated, the glass was placed under a UV lamp for 5 minutes with a light intensity of 250mW / cm 2 , with a wavelength of 365nm, a diffusion-enhanced, transparent, wear-resistant, and amphiphobic coating with a thickness of 50μm was obtained.

[0083] Example 3

[0084] The preparation method of the dispersion-strengthened transparent wear-resistant amphiphobic coating comprises the following steps:

[0085] (1) Synthesis of epoxy-modified SiO2 nanoparticles

[0086] 1 g of SiO2 nanoparticles with a particle size of 10-20 nm was dispersed in 99 g of anhydrous ethanol and ultrasonically treated for 30 min to break up the particle agglomerates to form a uniform dispersion. Subsequently, 0.1 g of KH560 and 0.1 g of water were added to the dispersion, and the pH was adjusted to 4 with acetic acid. The mixture was stirred at room temperature for 24 h to fully react. The solvent was removed by centrifugation, and the mixture was washed three times with ethanol to obtain epoxy-modified SiO2 nanoparticles.

[0087] (2) Synthesis of low surface energy resin

[0088] 12 g of ethyl orthosilicate, 3 g of γ-glycidyloxypropyltriethoxysilane, 3 g of phenyltriethoxysilane, 2 g of triethoxysilylethyl mono-terminated polydimethylsiloxane, 1 g of acetic acid, 3 g of water, and 5 g of ethanol were added to a 100 mL round-bottom flask, stirred at 70 ° C for 24 h, and then the solvent was removed by rotary evaporation to obtain a low surface energy resin.

[0089] (3) Preparation of light-curing coatings

[0090] Mix 10 g of low surface energy resin, 0.8 g of octavinyl POSS, 1.2 g of pentaerythritol tetraacrylate, 0.1 g of epoxy-modified SiO2 nanoparticles, 0.1 g of benzophenone, 0.1 g of diphenylformyl dimethyl benzyl ammonium salt, and 8 g of propylene glycol methyl ether acetate, and stir magnetically in the dark to obtain a light-curing coating.

[0091] (4) Preparation of dispersion-enhanced transparent wear-resistant amphiphilic coating

[0092] The prepared light-curing coating was dropped onto the glass surface, and naturally leveled. It was left at room temperature for 24 hours. After the solvent evaporated, the glass was placed under a UV lamp for 5 minutes with a light intensity of 250mW / cm 2 , with a wavelength of 365nm, a diffusion-enhanced, transparent, wear-resistant, and amphiphobic coating with a thickness of 50μm was obtained.

[0093] Example 4

[0094] The preparation method of the dispersion-strengthened transparent wear-resistant amphiphobic coating comprises the following steps:

[0095] (1) Synthesis of epoxy-modified SiO2 nanoparticles

[0096] 1 g of SiO2 nanoparticles with a particle size of 10-20 nm was dispersed in 99 g of anhydrous ethanol and ultrasonically treated for 30 min to break up the particle agglomerates to form a uniform dispersion. Subsequently, 0.1 g of KH560 and 0.1 g of water were added to the dispersion, and the pH was adjusted to 4 with acetic acid. The mixture was stirred at room temperature for 24 h to fully react. The solvent was removed by centrifugation, and the mixture was washed three times with ethanol to obtain epoxy-modified SiO2 nanoparticles.

[0097] (2) Synthesis of low surface energy resin

[0098] 7.5 g of ethyl orthosilicate, 7.5 g of γ-glycidyloxypropyltriethoxysilane, 2 g of methyltriethoxysilane, 2 g of phenyltriethoxysilane, 1 g of triethoxysilylethyl mono-terminated polydimethylsiloxane, 1 g of acetic acid, 3 g of water, and 5 g of ethanol were added to a 100 mL round-bottom flask, stirred at 70 ° C for 24 h, and then the solvent was removed by rotary evaporation to obtain a low surface energy resin.

[0099] (3) Preparation of light-curing coatings

[0100] 10 g of low surface energy resin, 1 g of octavinyl POSS, 0.15 g of epoxy-modified SiO2 nanoparticles, 0.1 g of benzophenone, 0.1 g of diphenylformyl dimethylbenzyl ammonium salt, and 8 g of butyl acetate were mixed and magnetically stirred in the dark to obtain a light-curing coating.

[0101] (4) Preparation of dispersion-enhanced transparent wear-resistant amphiphilic coating

[0102] The prepared light-curing coating was dropped onto the glass surface, and naturally leveled. It was left at room temperature for 24 hours. After the solvent evaporated, the glass was placed under a UV lamp for 5 minutes with a light intensity of 250mW / cm 2 , with a wavelength of 365nm, a diffusion-enhanced, transparent, wear-resistant, and amphiphobic coating with a thickness of 50μm was obtained.

[0103] Example 5

[0104] The preparation method of the dispersion-strengthened transparent wear-resistant amphiphobic coating comprises the following steps:

[0105] (1) Synthesis of epoxy-modified SiO2 nanoparticles

[0106] 1 g of SiO2 nanoparticles with a particle size of 10-20 nm was dispersed in 99 g of anhydrous ethanol and ultrasonically treated for 30 min to break up the particle agglomerates to form a uniform dispersion. Subsequently, 0.1 g of KH560 and 0.1 g of water were added to the dispersion, and the pH was adjusted to 4 with acetic acid. The mixture was stirred at room temperature for 24 h to fully react. The solvent was removed by centrifugation, and the mixture was washed three times with ethanol to obtain epoxy-modified SiO2 nanoparticles.

[0107] (2) Synthesis of low surface energy resin

[0108] 3 g of ethyl orthosilicate, 12 g of γ-glycidyloxypropyltriethoxysilane, 3 g of methyltriethoxysilane, 2 g of triethoxysilylethyl mono-terminated polydimethylsiloxane, 1 g of acetic acid, 3 g of water, and 5 g of ethanol were added to a 100 mL round-bottom flask, stirred at 70 ° C for 24 h, and then the solvent was removed by rotary evaporation to obtain a low surface energy resin.

[0109] (3) Preparation of light-curing coatings

[0110] 10 g of low surface energy resin, 1 g of octaepoxycyclohexylhexyl-cage POSS, 0.15 g of epoxy-modified SiO2 nanoparticles, 0.1 g of diphenylformyl dimethylbenzyl ammonium salt, and 8 g of butyl acetate were mixed and magnetically stirred in the dark to obtain a light-curing coating.

[0111] (4) Preparation of dispersion-enhanced transparent wear-resistant amphiphilic coating

[0112] The prepared photocurable coating was drop-coated onto the glass surface, leveled naturally, and left standing at room temperature for 24 h. After the solvent had evaporated, the glass slide was irradiated under an ultraviolet lamp for 5 min with a light intensity of 250 mW / cm 2 , a wavelength of 365 nm, to obtain a dispersion-strengthened transparent wear-resistant double-hydrophobic coating with a thickness of 50 μm.

[0113] Comparative Example 1

[0114] According to the preparation method of Example 1 of the present invention, the addition of epoxy-modified SiO2 nanoparticles was cancelled, and the other components and process parameters remained unchanged.

[0115] Comparative Example 2

[0116] According to the preparation method of Example 1 of the present invention, the epoxy-modified SiO2 nanoparticles were replaced with unmodified SiO2 nanoparticles, and the other components and process parameters remained unchanged.

[0117] Performance Test

[0118] (1) The following methods were used to test the performance of the dispersion-strengthened transparent wear-resistant double-hydrophobic coating prepared in Example 1:

[0119] 1. Optical properties: The transmittance of the coating surface was measured by an ultraviolet-visible spectrophotometer, and the results are as Figure 1 shown. Compared with the blank PET, the double-hydrophobic coating showed high transparency and had a certain antireflection effect. The coating was photographed with a camera, and the results are as Figure 2 shown.

[0120] 2. Hydrophobic property: The water contact angle of the coating surface was measured by a contact angle measuring instrument, and the results are as Figure 3 shown. The contact angle of the coating surface was about 106°, showing good hydrophobic characteristics.

[0121] 3. Oil resistance: A permanent marker was used to write the character "正" on the coating surface, and the handwriting was observed. The results are as Figure 4 shown. The ink of the character "正" was not continuous, indicating that a continuous oil film could not be formed on the coating surface, and the coating had oil repellency. Moreover, the ink could be gently wiped off with toilet paper without leaving a trace on the coating surface.

[0122] 4. Lubrication property: The friction coefficient of the coating surface was measured by a friction testing machine CSM. A polyester cloth was selected as the upper friction pair, the load was 1 N, and the frequency was 2 Hz. The results are as Figure 5 shown. Compared with the PET surface, the friction coefficient of the coating surface was greatly reduced to about 0.09, showing good slipperiness.

[0123] (2) The wear resistance of the dispersion-strengthened transparent wear-resistant amphiphobic coatings prepared in Examples 1 to 5 was tested using the following method:

[0124] The wear resistance of the coating was tested by abrasion tester. 0000# steel wool was used as the upper friction pair, the load was 10N, and the surface contact angle and morphology were tested after 1000 reciprocating frictions. The results are as follows Figure 6 After testing, no obvious wear marks were observed on the coating surfaces obtained in Examples 1 to 5.

[0125] (3) The basic physical and chemical parameters of the dispersion-strengthened, transparent, wear-resistant, and amphiphobic coatings obtained in Examples 1 to 5 were tested, and the results are shown in Table 1.

[0126] Table 1 Basic physical and chemical parameters of the dispersion-strengthened transparent wear-resistant amphiphobic coatings obtained in Examples 1 to 5

[0127] Pencil hardness (H) Elastic modulus (GPa) Transmittance (%) Friction coefficient Contact angle (°) Example 1 5 3.25 85.7％ 0.092 106 Example 2 3 2.98 85.9％ 0.095 103 Example 3 4 3.04 85.6％ 0.101 98 Example 4 4 3.15 85.3％ 0.111 101 Example 5 4 3.12 85.5％ 0.112 105 Comparative Example 1 2 1.75 85.2％ 0.103 103 Comparative Example 2 3 2.58 70.6％ 0.125 93

[0128] It can be seen that the dispersion-strengthened, transparent, wear-resistant, and double-repellent coatings prepared in Examples 1 to 5 have both excellent wear resistance and light transmittance. However, due to the lack of enhancement of epoxy-modified SiO2 nanoparticles in Comparative Example 1, the hardness of the coating is only 2H, the elastic modulus drops to 1.75GPa, and obvious wear marks appear on the surface after 1000 frictions. This is mainly because the lack of nanoparticles cannot fill the tiny defects inside the coating, which affects the stability of the coating network. The SiO2 nanoparticles in Comparative Example 2 are only doped into the coating network by physical mixing, and their compatibility is poor. The coating transmittance is only 70.6%, and the lack of epoxy functional groups causes a slight decrease in crosslinking degree. The elastic modulus of the coating is 2.58GPa. In addition, the Si-OH hydrophilic groups on the surface of the SiO2 nanoparticles affect the surface energy of the coating and inhibit the migration of polydimethylsiloxane segments to the surface, resulting in a higher friction coefficient (0.125) and a surface contact angle of 93°.

[0129] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing a dispersion-strengthened, transparent, wear-resistant, and amphiphobic coating, characterized in that: The following steps are involved: Mixing an organic silane compound, a small molecule acid, water and an alcohol solvent, performing a hydrolysis condensation reaction, and removing the solvent to obtain a low surface energy resin; the organic silane compound includes an orthosilicate compound, a triethoxysilane compound, γ-glycidyloxypropyltriethoxysilane and triethoxysilylethyl mono-terminated polydimethylsiloxane; The low surface energy resin, the crosslinking agent, the epoxy-modified SiO2 nanoparticles, the photoinitiator and the organic solvent are uniformly mixed to obtain a light-curing coating; The light-curing coating is coated on the surface of a substrate and subjected to ultraviolet light curing to obtain a diffusion-strengthened, transparent, wear-resistant, and amphiphobic coating.

2. The preparation method according to claim 1, characterized in that The orthosilicate compound includes ethyl orthosilicate and / or butyl orthosilicate; The triethoxysilane compound includes methyltriethoxysilane and / or phenyltriethoxysilane; The mass ratio of the orthosilicate compound, the triethoxysilane compound, γ-glycidyloxypropyltriethoxysilane and triethoxysilylethyl mono-terminated polydimethylsiloxane is (3-12):(3-4):(3-12):(1-2).

3. The preparation method according to claim 1 or 2, characterized in that The small molecule acid includes one or more of hydrochloric acid, nitric acid and acetic acid; The mass ratio of the organosilane compound to the small molecule acid is 20:1-3; The temperature of the hydrolysis condensation reaction is 60-80° C., and the time is 12-48 hours.

4. The preparation method according to claim 1, characterized in that The preparation method of the epoxy-modified SiO2 nanoparticles comprises the following steps: The alcohol dispersion of SiO2 nanoparticles is mixed with epoxy silane, the pH value of the mixture is adjusted to acidic, and a modification reaction is carried out to obtain epoxy-modified SiO2 nanoparticles.

5. The preparation method according to claim 4, characterized in that The particle size of the SiO2 nanoparticles is 10 to 20 nm.

6. The preparation method according to claim 4, characterized in that The epoxy silane includes 3-glycidyloxypropyltriethoxysilane and / or 3-glycidyloxypropyltrimethoxysilane; The mass ratio of the SiO2 nanoparticles to epoxy silane is 5 to 20:

1.

7. The preparation method according to claim 1, characterized in that The cross-linking agent comprises one or more of pentaerythritol tetraacrylate, pentaerythritol hexaacrylate, octavinyl POSS and octaepoxycyclohexyl hexyl-cage POSS; The photoinitiator includes one or more of benzophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, diphenylformyl dimethylbenzyl ammonium salt and bis(4-tert-butylphenyl)iodine hexafluorophosphate.

8. The preparation method according to claim 1 or 7, characterized in that The mass ratio of the low surface energy resin to the epoxy-modified SiO2 nanoparticles is 10:0.05-0.2; The mass ratio of the low surface energy resin to the crosslinking agent and the photoinitiator is 10:1-3:0.1-0.5; The mass ratio of the low surface energy resin to the organic solvent is 10:5-10.

9. The preparation method according to claim 1, characterized in that The intensity of the UV curing is 100-500 mW / cm 2 , time is 1 to 10 minutes.

10. The dispersion-strengthened, transparent, wear-resistant, and amphiphobic coating prepared by the preparation method according to any one of claims 1 to 9.

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