Organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating and preparation method and application thereof

Abstract

The application provides an organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating and a preparation method and application thereof, and belongs to the technical field of anti-fingerprint wear-resistant coating materials. The fluorine-free anti-fingerprint coating material modified by tung oil derivatives provided by the application is compounded by an organic-inorganic hybrid silicon resin, tung oil derivatives, a photoinitiator and an organic solvent, and is formed by ultraviolet light curing. The prepared organic-inorganic hybrid coating is a kind of transparent coating with low surface energy and high hardness. The coating can be quickly photocured to reach a surface dry state, and has high production efficiency; the coating does not contain fluorine and has environmental friendliness. The prepared coating has a water contact angle greater than 95 degrees, a light transmittance greater than 85 percent, and the fingerprint marks can be removed by wiping with a napkin for 3 times or less, and has excellent wear resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of anti-fingerprint wear-resistant coating materials, and particularly relates to an organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating and a preparation method and application thereof. BACKGROUND

[0002] Advanced multifunctional coatings have a wide range of applications in electronic displays, automotive windshields, automotive interiors, and the like. For example, the touch screen of a foldable smartphone or tablet computer requires a layer of transparent, hard and flexible coating to protect it from external mechanical scratches, impacts and bending. In addition, anti-fingerprint and anti-fouling performance are also very important in daily use, so a full-slip coating with oleophobic and hydrophobic functions is preferred. However, it is a great challenge to meet the above requirements simultaneously due to the inherent conflict between high hardness, high flexibility and full-slip. At the same time, for full-slip coatings, the surface needs to be carefully tailored to form nanoscale and microscale surface features or form special voids, but these methods are prone to cause low transparency and poor scratch resistance.

[0003] To solve these contradictions, developing an organic-inorganic hybrid coating is an effective way. Specifically, silane-derived silicon-based materials are the basis of such coatings, because siloxane can form an inorganic Si-O core, providing glass-like hardness, while other organic groups can endow the coating with flexibility and the desired functionality. Acrylic monomers and oligomers, as a commonly used ultraviolet light curing reactive diluent, have been widely used in ultraviolet light coatings or formulations. However, most acrylic monomers or oligomers (such as hydroxyethyl acrylate, diethylene glycol diacrylate, trimethylpropyl acrylate, pentaerythritol triacrylate, etc.) have the disadvantages of high volatility, skin irritation, poor odor, etc., which greatly limit the application range of these materials. Combining acrylic reactive monomers with other organic materials to form new ultraviolet light curing reactive monomers can effectively overcome the above shortcomings, such as combining tung oil with acrylate reactive monomers to prepare low-volatility, low-viscosity, high-reactivity ultraviolet light curing reactive monomers is a good choice, which can well meet the requirements of industrial applications.

[0004] For example, patent CN113372803A discloses a kind of anticorrosive ice-prevention self-cleaning super-hydrophobic coating and its preparation method and application, the invention uses 1H, 1H, 2H, 2H- perfluorodecyl trimethoxysilane to modify SiO2 hydrophobic, reduce its surface energy, then use modified SiO2 doped polyester type thermoplastic polyurethane elastomer to prepare the anticorrosive self-cleaning super-hydrophobic coating with good hydrophobic performance, which can effectively improve the hydrophobicity of metal equipment surface and improve its anti-icing performance. The patent has the disadvantage that the coating formed on the surface is not wear-resistant, the stability is poor, and toxic fluorine-containing compounds are used in the preparation process. Patent CN106146754A introduces a preparation method of a 3D printing silicon-containing nanogel photocuring resin and its application, prepares and mixes acryloxy-containing silicone resin prepolymer, acryloxy-modified white carbon black as reinforcing filler, photoinitiator and the like to obtain a photocuring silicon resin prepolymer, which can be obtained by photopolymerization. 3D printing ultraviolet light-cured transparent silicon resin composite material has good ultraviolet radiation resistance, thermal stability, weather resistance, electrical insulation, hydrophobicity and flame retardancy. However, a large amount of solvent is required in the preparation process, and a large amount of powder is contained, which is not environmentally friendly. Patent CN104530852A discloses a preparation of a high-hydrophobic fluorocarbon coating for photovoltaic module backsheet, provides a preparation process simple, and the hydrophobic modified nano-silicon dioxide is uniformly dispersed in the main resin. After being coated on the substrate, a micro-nano rough texture structure is formed, which, combined with the low surface energy of fluorocarbon resin itself, makes the surface have the high hydrophobicity of "lotus leaf effect", avoids the adhesion of dew, rainwater and water vapor on the surface of the backsheet, improves the hydrolysis resistance of the backsheet, and has good antifouling effect. However, the patent uses hydrophobic particles mixed with fluorocarbon resin, which is difficult to mix, and the uniformity of the coating cannot be guaranteed, which has an adverse effect on the light transmission performance and mechanical properties. And using fluorocarbon resin as the main resin contains a large amount of fluorine element, which is not conducive to environmental protection and has high cost. The above hydrophobic coating introduces toxic fluorine-containing groups or adds a large amount of powder to achieve hydrophobic effect, which reduces the stability, wear resistance and transmittance of the coating. In view of the problems existing in the prior art, a fluorine-free, transparent and hydrophobic wear-resistant coating needs to be developed. SUMMARY

[0005] The purpose of the present application is to provide an organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating and its preparation method and application, to solve the technical problems of low wear resistance, anti-fingerprint and low transmittance of the existing hydrophobic coating.

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

[0007] The present application provides a preparation method of an organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating, comprising the following steps:

[0008] 1) mixing organic-inorganic hybrid silicone resin, tung oil derivative, photoinitiator and organic solvent to obtain mixed coating;

[0009] 2) applying the mixed coating on the substrate and performing ultraviolet curing to obtain the organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating.

[0010] Further, the preparation method of the organic-inorganic hybrid silicone resin comprises the following steps:

[0011] mixing siloxane, tetraethyl silicate and silane coupling agent in acidic solvent to hydrolyze to obtain the organic-inorganic hybrid silicone resin;

[0012] The molar ratio of the siloxane, tetraethyl silicate and silane coupling agent is 1:0.2-9:0.2-9.

[0013] Further, the siloxane comprises one or more of trimethylchlorosiloxane, tetramethyldivinyl disiloxane, vinylpentamethyldisiloxane, trimethylmethoxysilane, trimethylethoxysilane, hexamethyldisiloxane, dimethyldimethoxysilane and dimethyldiethoxysilane;

[0014] The silane coupling agent comprises one or more of γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, methyltriethoxysilane and methyltrimethoxysilane;

[0015] The acid in the acidic solvent comprises one or more of methylbenzenesulfonic acid, oxalic acid, hydrochloric acid and acetic acid; the solvent in the acidic solvent comprises at least two of toluene, methanol, ethanol, ethylene glycol, glycerol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, chloroform, tetrahydrofuran, butyl acetate, dimethyl sulfoxide, isopropyl alcohol and water, and the amount of the acidic solvent is 10-60% of the total mass of the siloxane, tetraethyl silicate and silane coupling agent.

[0016] Further, the temperature of the hydrolysis is 25-90℃, and the time of the hydrolysis is 6-24h.

[0017] Further, the preparation method of the tung oil derivative comprises the following steps:

[0018] Mixing tung oil anhydride, acrylic ester monomer and polymerization inhibitor, under the action of heating and catalyst, tung oil derivative is obtained by reaction;

[0019] The molar ratio of the tung oil anhydride to the acrylic ester monomer is 1:5-7, the content of the polymerization inhibitor is 0.5-5% of the total mass of the tung oil anhydride and the acrylic ester monomer, and the mass of the catalyst is 0.1-2% of the total mass of the tung oil anhydride and the acrylic ester monomer;

[0020] The mass of the tung oil derivative is 1-50% of the total mass of the organic-inorganic hybrid silicon resin and the tung oil derivative.

[0021] Further, the acrylic ester monomer comprises one or more of hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycidyl methacrylate, 2-ethoxyethyl acrylate, 2-cyanoacrylate, beta-hydroxypropyl acrylate, beta-hydroxypropyl methacrylate, dipentaerythritol pentaacrylate and pentaerythritol triacrylate; the polymerization inhibitor comprises one or more of hydroquinone, p-hydroxyanisole and methylhydroquinone; and the catalyst comprises p-toluenesulfonic acid and / or N,N-dimethylethanolamine.

[0022] The temperature of the reaction is 60-100 DEG C, and the reaction time is 4-12 h.

[0023] Further, the photoinitiator comprises one or more of photoinitiator 250, photoinitiator 6992, photoinitiator BDK, photoinitiator 369, photoinitiator MBF, photoinitiator PBZ, photoinitiator EDB, photoinitiator 379, photoinitiator 784, photoinitiator 2959, photoinitiator 184-L, photoinitiator TPO, photoinitiator TPO-L and photoinitiator 1173; and the mass of the photoinitiator is 1-5% of the total mass of the organic-inorganic hybrid silicon resin and the tung oil derivative.

[0024] Further, the organic solvent comprises one or more of acetone, tetrahydrofuran, ethanol, methanol, ethyl acetate, n-butyl acetate, chloroform, dichloromethane, dimethyl sulfoxide, propylene glycol methyl ether, ethylene glycol butyl ether, n-pentane and toluene; and the mass of the organic solvent is 1-10 times of the total mass of the organic-inorganic hybrid silicon resin and the tung oil derivative.

[0025] The application provides an organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating.

[0026] The application also provides application of the organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating in anti-fingerprint self-cleaning wear-resistant materials.

[0027] The application has the following beneficial effects:

[0028] The application provides a tung oil derivative modified fluorine-free anti-fingerprint wear-resistant transparent coating which is configured into a solution by tung oil derivative, organic-inorganic hybrid silicone resin, photoinitiator and organic solvent, is sprayed on a substrate by a spray gun, is cured by ultraviolet light to form a film, has high hardness and transparency due to the organic-inorganic hybrid silicone resin itself, and has low surface energy, but the pure silicone resin coating is prone to cracking, so a flexible chain segment needs to be introduced into the silicone resin, and therefore the tung oil which is flexible and hydrophobic is introduced to make the film have good hydrophobic performance, wear resistance and anti-fingerprint performance without cracking.

[0029] The application uses the organic-inorganic hybrid silicone resin, introduces tetraethyl silicate while synthesizing the organic silicone resin with high crosslinking degree in the molecule, and the tetraethyl silicate has small steric hindrance and can be self-condensed to form a "hard core" more quickly, so as to provide the silicone resin with the strength similar to that of quartz, and the silane coupling agent and the siloxane form a branched structure, so that the silicone resin has a crosslinked molecular structure coexisting with the spherical and branched chain segments, and the structure can make the material have higher hardness. Meanwhile, the silicone resin itself has low surface energy, so that the material has good hydrophobic performance, is fluorine-free, low-toxicity and pollution-free, and is more environmentally friendly.

[0030] The coating of the application has the characteristics of low cost, low toxicity and renewable biological resources, and the tung oil can be extracted from the seeds of tung trees and has a wide source of monomers. Meanwhile, the preparation method is simple, ultraviolet light curing is adopted, and the preparation process is more green and environmentally friendly. DETAILED DESCRIPTION

[0031] The application provides a preparation method of an organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating, which comprises the following steps.

[0032] 1) mixing the organic-inorganic hybrid silicone resin, the tung oil derivative, the photoinitiator and the organic solvent to obtain a mixed coating;

[0033] 2) coating the mixed coating on a substrate and performing ultraviolet light curing to obtain the organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating.

[0034] In the application, the preparation method of the organic-inorganic hybrid silicone resin comprises the following steps.

[0035] mixing the siloxane, the tetraethyl silicate and the silane coupling agent in an acidic solvent to hydrolyze to obtain the organic-inorganic hybrid silicone resin;

[0036] The molar ratio of the siloxane, the tetraethyl silicate and the silane coupling agent is 1:0.2-9:0.2-9, preferably 1:1-8:1-8, further preferably 1:1.5-6:1.5-5, and more preferably 1:1.6:2.3.

[0037] In the present application, the silane coupling agent and the siloxane are preferably configured into a solution first, and then tetraethyl silicate is added to obtain an organic-inorganic hybrid silicone resin.

[0038] In the present application, the siloxane is preferably one or more of trimethyl chlorosiloxane, tetramethyl divinyl disiloxane, vinyl pentamethyl disiloxane, trimethyl methoxysilane, trimethyl ethoxysilane, hexamethyl disiloxane, dimethyl dimethoxysilane and dimethyl diethoxysilane.

[0039] The silane coupling agent is preferably one or more of γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl triethoxysilane, γ-mercaptopropyl trimethoxysilane, γ-mercaptopropyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyl trimethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, dodecyl trimethoxysilane, dodecyl triethoxysilane, hexadecyl trimethoxysilane, hexadecyl triethoxysilane, methyl triethoxysilane and methyl trimethoxysilane; when the silane coupling agent is two of the above, the present application does not have special provisions for the ratio of different types of silane coupling agents, which can be adjusted according to actual needs.

[0040] The acid in the acidic solvent is preferably one or more of methylbenzenesulfonic acid, oxalic acid, hydrochloric acid and acetic acid; when the acid is two of the above, the present application does not have special provisions for the ratio of different types of acids, which can be adjusted according to actual needs.

[0041] In the present application, the solvent in the acidic solvent is preferably at least two of toluene, methanol, ethanol, ethylene glycol, glycerol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, chloroform, tetrahydrofuran, butyl acetate, dimethyl sulfoxide, isopropyl alcohol and water, preferably a mixed solvent formed by mixing one of toluene, methanol, ethanol, ethylene glycol, glycerol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, chloroform, tetrahydrofuran, butyl acetate, dimethyl sulfoxide, isopropyl alcohol and water, more preferably a mixed solvent of ethanol and water, and the molar ratio of ethanol to water is 1:2.

[0042] In the present application, the amount of the acidic solvent is 10-60% of the total mass of the siloxane, tetraethyl silicate and silane coupling agent, preferably 35-50%, and more preferably 40-45%.

[0043] In the present application, the hydrolysis is carried out under stirring, the stirring speed is 500-1000 rpm, preferably 800 rpm; the temperature of the hydrolysis is 25-90℃, preferably 30-80℃, further preferably 40-60℃; the time of the hydrolysis is 6-24 h, preferably 6-12 h, further preferably 8-10 h.

[0044] In the present application, the preparation method of the tung oil derivative comprises the following steps:

[0045] The tung oil anhydride, the acrylate monomer and the polymerization inhibitor are mixed, and the tung oil derivative is obtained by reaction under the action of heating and catalyst;

[0046] The molar ratio of the tung oil anhydride to the acrylate monomer is 1:5-7, preferably 1:6; the content of the polymerization inhibitor is 0.5-5% of the total mass of the tung oil anhydride and the acrylate monomer, preferably 1-3%, further preferably 2%; the mass of the catalyst is 0.1-2% of the total mass of the tung oil anhydride and the acrylate monomer, preferably 0.5-1%, further preferably 0.8%;

[0047] The mass of the tung oil derivative is 1-50% of the total mass of the organic-inorganic hybrid silicone resin and the tung oil derivative, preferably 10-40%, further preferably 20-30%.

[0048] In the present application, the acrylate monomer is preferably one or more of hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycidyl methacrylate, 2-ethoxyethyl acrylate, 2-cyanoacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, dipentaerythritol pentaacrylate and pentaerythritol triacrylate; the polymerization inhibitor is preferably one or more of hydroquinone, p-hydroxyanisole and methylhydroquinone; the catalyst is preferably p-toluenesulfonic acid and / or N,N-dimethylethanolamine.

[0049] In the present application, the reaction is carried out under stirring, the stirring speed is 200-500 rpm, preferably 400 rpm, the temperature of the reaction is 60-100℃, preferably 70-90℃, further preferably 75-85℃; the time of the reaction is 4-12 h, preferably 4-10 h, further preferably 5-9 h, more preferably 6-8 h.

[0050] In the present application, the photoinitiator is preferably one or several of photoinitiator 250, photoinitiator 6992, photoinitiator BDK, photoinitiator 369, photoinitiator MBF, photoinitiator PBZ, photoinitiator EDB, photoinitiator 379, photoinitiator 784, photoinitiator 2959, photoinitiator 184-L, photoinitiator TPO, photoinitiator TPO-L and photoinitiator 1173; the mass of the photoinitiator is 1-5% of the total mass of the organic-inorganic hybrid silicone resin and the tung oil derivative, preferably 1.4-4%, and further preferably 1.5-2.5%.

[0051] In the present application, the organic solvent is preferably one or several of acetone, tetrahydrofuran, ethanol, methanol, ethyl acetate, n-butyl acetate, chloroform, dichloromethane, dimethyl sulfoxide, propylene glycol methyl ether, ethylene glycol butyl ether, n-pentane and toluene; the mass of the organic solvent is 1-10 times, preferably 1.5-5 times, and further preferably 2-3 times of the total mass of the organic-inorganic hybrid silicone resin and the tung oil derivative.

[0052] In the present application, the substrate is not particularly limited, and the present application can be used to form a film on the surface of a well-known coating substrate (plastic, glass, composite material, film, metal); in the examples of the present application, the substrate used is a glass slide.

[0053] The present application uses a spraying or scraping method to apply the mixed coating on the surface of the substrate, and then performs ultraviolet curing to obtain an organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating.

[0054] In the present application, in the spraying method, the spraying pressure is preferably 0.1-3 MPa, more preferably 0.2-2 MPa, and further preferably 0.25-0.3 MPa. In the present application, the coating amount of the mixed coating on the substrate is preferably 0.001-0.005 g / cm 3 .

[0055] In the present application, the ultraviolet curing is preferably performed under a UV-LED lamp, and the ultraviolet curing time is preferably 30-900 s, more preferably 60-300 s, and further preferably 60-150 s.

[0056] In the ultraviolet curing process, the photoinitiator absorbs ultraviolet light and converts into free radicals, which initiates the crosslinking of the active groups in the silicone resin, so that the coating is cured.

[0057] The present application provides an organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating.

[0058] The present application also provides an application of the organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating in anti-fingerprint self-cleaning wear-resistant materials.

[0059] The technical solutions provided by the present application are described in detail below in conjunction with examples, but they should not be understood as limiting the scope of protection of the present application.

[0060] Example 1

[0061] (1) Put the glass slide in water and use an ultrasonic cleaner to ultrasonically clean for 15 min, and then put the substrate in ethanol and use an ultrasonic cleaner to ultrasonically clean for 15 min. The substrate with a clean surface is obtained.

[0062] (2) Add 1 g of tung oil derivative, 0.4 g of photoinitiator 184-L, and 20 g of ethanol to 9 g of organic-inorganic hybrid silicone resin, and stir uniformly to obtain a mixed coating;

[0063] (3) Spray the mixed coating on the cleaned glass slide at a pressure of 0.25 MPa;

[0064] (4) Put the glass slide sprayed with the mixed coating into a UV-LED lamp and irradiate with ultraviolet light for 90 s to obtain a transparent coating.

[0065] The preparation process of the organic-inorganic hybrid silicone resin includes the following steps:

[0066] Take a single-neck round-bottom flask, first add 6.00 g of ethanol and 4.68 g of deionized water, then add 0.25 g of acetic acid, 1.81 g of dimethyl dimethoxy silane, 16.38 g of gamma-methacryloxypropyl trimethoxy silane, and 10.24 g of tetraethyl silicate, and stir at a magnetic stirring speed of 800 rpm and a temperature of 40℃ for 6 h. The structure of the obtained organic-inorganic hybrid silicone resin is as follows:

[0067]

[0068] wherein R is or CH3;

[0069] The preparation process of the tung oil derivative includes the following steps:

[0070] Under nitrogen protection, tung oil anhydride and N,N-dimethyl ethanolamine accounting for 1% of the total mass of the system are added to a three-necked flask, mechanically stirred at 400 rpm and heated, and when the temperature rises to 70℃, 6 times the molar amount of hydroxyethyl methacrylate and hydroxyethyl methacrylate, and 1% of the total mass of the system of p-hydroxyanisole are added dropwise. The temperature is raised to 100℃ and reacted for 6 h. The structure of the obtained tung oil derivative T6 is as follows:

[0071]

[0072] Example 2

[0073] (1) Put the glass slide in water and use the ultrasonic cleaner to clean for 15 min, then put the substrate in ethanol and use the ultrasonic cleaner to clean for 15 min. Get the clean substrate.

[0074] (2) Add 1 g of tung oil derivative, 0.4 g of photoinitiator 184-L, and 20 g of ethanol into 9 g of organic-inorganic hybrid silicone resin, and stir to get the mixed coating;

[0075] (3) Spray the mixed coating on the clean glass slide at a pressure of 0.25 MPa;

[0076] (4) Put the glass slide sprayed with the mixed coating into the UV-LED lamp and irradiate for 90 s to get the transparent coating.

[0077] The preparation process of the organic-inorganic hybrid silicone resin includes the following steps:

[0078] Take a single-necked round-bottom flask, first add 6.00 g of ethanol and 4.68 g of deionized water, then add 0.15 g of hydrochloric acid, 3.24 g of trimethylchlorosilane, 16.38 g of γ-methacryloxypropyltrimethoxysilane, and 10.24 g of tetraethyl silicate, and stir at a magnetic stirring speed of 800 rpm and a temperature of 40℃ for 6 h. The structure of the obtained organic-inorganic hybrid silicone resin is as follows:

[0079]

[0080] wherein R is or CH3;

[0081] The preparation process of the tung oil derivative includes the following steps:

[0082] Under nitrogen protection, add tung oil anhydride and N,N-dimethyl ethanolamine accounting for 1% of the total mass of the system into a three-necked flask, mechanically stir at 400 rpm and heat, when the temperature rises to 70℃, add hydroxyethyl methacrylate and hydroxyethyl methacrylate with a molar amount of 6 times that of tung oil anhydride, and p-hydroxyanisole accounting for 1% of the total mass of the system. Increase the temperature to 100℃ and react for 6 h. The structure of the obtained tung oil derivative T6 is as follows:

[0083]

[0084] Example 3

[0085] (1) Put the glass slide in water and use the ultrasonic cleaner to clean for 15 min, then put the substrate in ethanol and use the ultrasonic cleaner to clean for 15 min. Get the clean substrate.

[0086] (2) 1 g of the tung oil derivative, 0.4 g of the photoinitiator 184-L, and 20 g of ethanol were added into 9 g of the organic-inorganic hybrid silicone resin to obtain a mixed coating, wherein the tung oil derivative was the tung oil derivative in Example 1.

[0087] (3) The mixed coating was sprayed on a clean glass slide at a pressure of 0.25 MPa.

[0088] (4) The glass slide sprayed with the mixed coating was placed under a UV-LED lamp for UV irradiation for 90 s to obtain a transparent coating.

[0089] The preparation process of the organic-inorganic hybrid silicone resin includes the following steps:

[0090] A single-mouth round-bottom flask was taken, 6.00 g of ethanol and 4.68 g of deionized water were first added, then 0.25 g of acetic acid, 2.44 g of hexamethyldisiloxane, 16.38 g of γ-methacryloxypropyltrimethoxysilane, 1.73 g of hexadecyltrimethoxysilane, and 10.24 g of tetraethyl silicate were added, the magnetic stirring speed was 800 rpm, the temperature was 40°C, and the reaction was carried out for 6 h. The structure of the obtained organic-inorganic hybrid silicone resin is as follows:

[0091]

[0092] wherein R is or CH3;

[0093] Example 4

[0094] (1) The glass slide was placed in water and cleaned using an ultrasonic cleaner for 15 min, and then the substrate was placed in ethanol and cleaned using an ultrasonic cleaner for 15 min. A clean substrate was obtained.

[0095] (2) 1 g of the tung oil derivative, 0.4 g of the photoinitiator 184-L, and 20 g of ethanol were added into 9 g of the organic-inorganic hybrid silicone resin to obtain a mixed coating, wherein the tung oil derivative was the tung oil derivative in Example 1.

[0096] (3) The mixed coating was sprayed on a clean glass slide at a pressure of 0.25 MPa.

[0097] (4) The glass slide sprayed with the mixed coating was placed under a UV-LED lamp for UV irradiation for 90 s to obtain a transparent coating.

[0098] The preparation process of the organic-inorganic hybrid silicone resin includes the following steps:

[0099] A single-necked round bottom flask was charged with 6.00 g of ethanol and 4.68 g of deionized water, followed by 0.15 g of hydrochloric acid, 3.24 g of trimethylchlorosilane, 16.38 g of gamma-methacryloxypropyltrimethoxysilane, 1.73 g of hexadecyltrimethoxysilane, and 10.24 g of tetraethyl orthosilicate. The reaction was carried out at 800 rpm of magnetic stirring speed and 40°C for 6 h. The structure of the obtained organic-inorganic hybrid silicone resin is as follows:

[0100]

[0101] wherein R is or CH3;

[0102] Example 5

[0103] (1) The glass slide was placed in water and cleaned using an ultrasonic cleaner for 15 min, and then the substrate was placed in ethanol and cleaned using an ultrasonic cleaner for 15 min. A clean substrate was obtained.

[0104] (2) 2 g of tung oil derivative, 0.4 g of photoinitiator 184-L, and 20 g of ethanol were added to 8 g of the organic-inorganic hybrid silicone resin to obtain a mixed coating, wherein the organic-inorganic hybrid silicone resin was the organic-inorganic hybrid silicone resin of Example 3, and the tung oil derivative was the tung oil derivative of Example 1.

[0105] (3) The mixed coating was sprayed on the cleaned glass slide at a pressure of 0.25 MPa.

[0106] (4) The glass slide sprayed with the mixed coating was placed under a UV-LED lamp for ultraviolet irradiation for 90 s to obtain a transparent coating.

[0107] Example 6

[0108] (1) The glass slide was placed in water and cleaned using an ultrasonic cleaner for 15 min, and then the substrate was placed in ethanol and cleaned using an ultrasonic cleaner for 15 min. A clean substrate was obtained.

[0109] (2) 3 g of tung oil derivative, 0.4 g of photoinitiator 184-L, and 20 g of ethanol were added to 7 g of the organic-inorganic hybrid silicone resin to obtain a mixed coating, wherein the organic-inorganic hybrid silicone resin was the organic-inorganic hybrid silicone resin of Example 3, and the tung oil derivative was the tung oil derivative of Example 1.

[0110] (3) The mixed coating was sprayed on the cleaned glass slide at a pressure of 0.25 MPa.

[0111] (4) The glass slide sprayed with the mixed coating was placed under UV-LED lamp for UV irradiation for 90s to obtain a transparent coating layer.

[0112] Comparative Example 1

[0113] (1) The glass slide was placed in water and cleaned using an ultrasonic cleaner for 15 min, and then the substrate was placed in ethanol and cleaned using an ultrasonic cleaner for 15 min. A clean substrate was obtained.

[0114] (2) 0.4 g of photoinitiator 184-L and 20 g of ethanol were added to 10 g of organic-inorganic hybrid silicone resin, and the mixture was stirred to obtain a mixed coating, wherein the organic-inorganic hybrid silicone resin was the silicone resin in Example 1.

[0115] (3) The mixed coating was sprayed on the clean glass slide at a pressure of 0.25 MPa.

[0116] (4) The glass slide sprayed with the mixed coating was placed under UV-LED lamp for UV irradiation for 90s to obtain a transparent coating layer.

[0117] Comparative Example 2

[0118] (1) The glass slide was placed in water and cleaned using an ultrasonic cleaner for 15 min, and then the substrate was placed in ethanol and cleaned using an ultrasonic cleaner for 15 min. A clean substrate was obtained.

[0119] (2) 0.4 g of photoinitiator 184-L and 20 g of ethanol were added to 10 g of organic-inorganic hybrid silicone resin, and the mixture was stirred to obtain a mixed coating, wherein the organic-inorganic hybrid silicone resin was the silicone resin in Example 2.

[0120] (3) The mixed coating was sprayed on the clean glass slide at a pressure of 0.25 MPa.

[0121] (4) The glass slide sprayed with the mixed coating was placed under UV-LED lamp for UV irradiation for 90s to obtain a transparent coating layer.

[0122] Comparative Example 3

[0123] (1) The glass slide was placed in water and cleaned using an ultrasonic cleaner for 15 min, and then the substrate was placed in ethanol and cleaned using an ultrasonic cleaner for 15 min. A clean substrate was obtained.

[0124] (2) 0.4 g of photoinitiator 184-L and 20 g of ethanol were added to 10 g of organic-inorganic hybrid silicone resin, and the mixture was stirred to obtain a mixed coating, wherein the organic-inorganic hybrid silicone resin was the silicone resin in Example 3.

[0125] (3) The mixed coating was sprayed on a clean glass slide at a pressure of 0.25 MPa;

[0126] (4) The glass slide with the mixed coating was placed under a UV-LED lamp for 90 s to obtain a transparent coating.

[0127] Comparative Example 4

[0128] (1) The glass slide was placed in water and cleaned using an ultrasonic cleaner for 15 min, and then the substrate was placed in ethanol and cleaned using an ultrasonic cleaner for 15 min to obtain a clean substrate.

[0129] (2) 0.4 g of photoinitiator 184-L, 20 g of ethanol were added to 10 g of organic-inorganic hybrid silicone resin to obtain a mixed coating, wherein the organic-inorganic hybrid silicone resin was the silicone resin in Example 4.

[0130] (3) The mixed coating was sprayed on a clean glass slide at a pressure of 0.25 MPa;

[0131] (4) The glass slide with the mixed coating was placed under a UV-LED lamp for 90 s to obtain a transparent coating.

[0132] Performance test:

[0133] (1) Contact angle test: The contact angle of the coating prepared in Examples 1-6 and Comparative Examples 1-4 was measured using a standard contact angle meter, and the results are shown in Table 1.

[0134] (2) Fingerprint resistance test: The artificial fingerprint fluid was composed of 95% artificial sweat and 5% artificial sebum. The artificial sweat was prepared by mixing lactic acid 3 mL / L, acetic acid 5 mL / L, sodium chloride 10 g / L, sodium hydrogen phosphate 10 g / L and deionized water. The artificial sebum was composed of oleic acid (2%), stearic acid (2%), and squalene (1%). A small amount of non-ionic surfactant (Triton X100, added amount 2 μL / g of the mixture) was added to overcome the natural immiscibility between sweat and sebum. First, the finger was cleaned with alcohol, then the finger was immersed in the artificial fingerprint fluid, then the fingerprint was formed on the surface of the coating by touching, and then the fingerprint was wiped with a paper towel at a speed of 3 cm / s under a load of 500 g, and the number of wipes that could make the fingerprint disappear was recorded. The results are shown in Table 1.

[0135] (3) Pencil hardness test: According to the requirements of ASTM D3363, a series of pencils with hardness from 6B to 9H were used to measure the hardness of the coating.

[0136] (4) Abrasion resistance test: Steel wool was used to cyclically rub the sample under 500g load at a speed of 3cm / s for 500 times. The water contact angle of the sample after rubbing was measured.

[0137] (5) Transmittance test: UV-Vis spectrophotometer was used to measure the transmittance of different coatings. The transmittance at 550nm was used as the standard. The results are shown in Table 1.

[0138] Table 1 Water contact angle, pencil hardness, anti-fingerprint property, abrasion resistance and transmittance of the coatings prepared in Examples 1-6 and Comparative Examples 1-4.

[0139]

[0140]

[0141] From the above examples and experimental data in Table 1, it can be seen that the present application provides an organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating and its preparation method and application. The organic-inorganic hybrid coating prepared by the present application is a transparent coating with low surface energy and high hardness. The coating can be quickly photocured to reach the surface dry state, and the production efficiency is high. The coating does not contain fluorine and is environmentally friendly. The prepared coating has a water contact angle greater than 95°, a light transmittance greater than 85%, and the fingerprint marks can be removed after 3 or fewer times of wiping with a napkin, and has excellent abrasion resistance.

[0142] The above description is only the preferred embodiments of the present application. It should be noted that for those skilled in the art, without departing from the principles of the present application, several improvements and refinements can be made, which should also be considered within the scope of protection of the present application.

Claims

1. A method for preparing an organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating, characterized in that: The following steps are involved: 1) mixing an organic-inorganic hybrid silicone resin, a tung oil derivative, a photoinitiator, and an organic solvent to obtain a mixed coating; 2) applying the mixed coating on a substrate and curing it with ultraviolet light to obtain an organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating; The preparation method of the organic-inorganic hybrid silicone resin comprises the following steps: Siloxane, tetraethyl silicate and a silane coupling agent are mixed in an acidic solvent and hydrolyzed to obtain an organic-inorganic hybrid silicone resin; The molar ratio of the siloxane, tetraethyl silicate and silane coupling agent is 1:0.2~9:0.2~9; The siloxane comprises one or more of trimethylchlorosiloxane, tetramethyldivinyldisiloxane, vinylpentamethyldisiloxane, trimethylmethoxysilane, trimethylethoxysilane, hexamethyldisiloxane, dimethyldimethoxysilane and dimethyldiethoxysilane; The preparation method of the tung oil derivative comprises the following steps: Tung oil anhydride, acrylate monomer and polymerization inhibitor are mixed and reacted under heating and the action of a catalyst to obtain a tung oil derivative; The molar ratio of tung oil anhydride to acrylate monomer is 1:5-7, the content of the polymerization inhibitor is 0.5-5% of the total mass of tung oil anhydride and acrylate monomer, and the mass of the catalyst is 0.1-2% of the total mass of tung oil anhydride and acrylate monomer; The mass of the tung oil derivative is 1-50% of the total mass of the organic-inorganic hybrid silicone resin and the tung oil derivative.

2. The preparation method according to claim 1, characterized in that The silane coupling agent comprises one or more of γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, methyltriethoxysilane and methyltrimethoxysilane; The acid in the acidic solvent comprises one or more of toluenesulfonic acid, oxalic acid, hydrochloric acid and acetic acid; the solvent in the acidic solvent comprises at least two of toluene, methanol, ethanol, ethylene glycol, glycerol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, chloroform, tetrahydrofuran, butyl acetate, dimethyl sulfoxide, isopropanol and water, and the amount of the acidic solvent is 10-60% of the total mass of the siloxane, tetraethyl silicate and silane coupling agent.

3. The preparation method according to claim 2, characterized in that The hydrolysis temperature is 25-90° C., and the hydrolysis time is 6-24 hours.

4. The preparation method according to claim 3, characterized in that The acrylate monomer comprises one or more of hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycidyl methacrylate, 2-ethoxyethyl acrylate, 2-cyanoacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, dipentaerythritol pentaacrylate, and pentaerythritol triacrylate; the polymerization inhibitor comprises one or more of hydroquinone, p-hydroxyanisole, and methylhydroquinone; and the catalyst comprises p-toluenesulfonic acid and / or N, N-dimethylethanolamine; The reaction temperature is 60-100° C., and the reaction time is 4-12 hours.

5. The preparation method according to claim 1, 2 or 4, characterized in that: The photoinitiator comprises one or more of photoinitiator 250, photoinitiator 6992, photoinitiator BDK, photoinitiator 369, photoinitiator MBF, photoinitiator PBZ, photoinitiator EDB, photoinitiator 379, photoinitiator 784, photoinitiator 2959, photoinitiator 184-L, photoinitiator TPO, photoinitiator TPO-L and photoinitiator 1173; the mass of the photoinitiator is 1-5% of the total mass of the organic-inorganic hybrid silicone resin and the tung oil derivative.

6. The preparation method according to claim 5, characterized in that The organic solvent comprises one or more of acetone, tetrahydrofuran, ethanol, methanol, ethyl acetate, n-butyl acetate, chloroform, dichloromethane, dimethyl sulfoxide, propylene glycol methyl ether, ethylene glycol butyl ether, n-pentane and toluene; the mass of the organic solvent is 1 to 10 times the total mass of the organic-inorganic hybrid silicone resin and the tung oil derivative.

7. The organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating prepared by the preparation method according to any one of claims 1 to 6.

8. Use of the organic-inorganic hybrid fluorine-free anti-fingerprint transparent coating according to claim 7 in anti-fingerprint self-cleaning wear-resistant materials.

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