A plant oil modified fluorine-free anti-fingerprint transparent coating material, a preparation method and application thereof

Abstract

The application provides a plant oil modified fluorine-free anti-fingerprint transparent coating material and a preparation method and application thereof, and belongs to the technical field of anti-fingerprint coating materials.The plant oil modified fluorine-free anti-fingerprint transparent coating material is prepared from an organic silicon modified polyurethane acrylate prepolymer, plant oil, a photoinitiator, an organic solvent and hydrophobic nanoparticles, and is formed through ultraviolet light curing.The prepared organic silicon modified polymer coating has low surface energy and environmental protection, can be rapidly photocured to reach a surface dry state under ultraviolet light irradiation, improves production efficiency, and has transparency, excellent hydrophobic effect and anti-fingerprint performance.The results of the examples show that the water contact angle is more than 100 degrees, the light transmittance is more than 80 percent, and the anti-fingerprint performance of removing fingerprint marks by wiping with a paper towel for 3 times or less.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of anti-fingerprint coating materials, in particular to a plant oil modified fluorine-free anti-fingerprint transparent coating material and a preparation method and application thereof. BACKGROUND

[0002] In recent years, with the increasingly prominent environmental problems, people's requirements for energy consumption and environmental protection are becoming higher and higher. Photocuring technology is a very important polymerization method through irradiation of light source to make monomers or resins crosslink. Compared with traditional thermal curing, ultraviolet photocuring technology has the characteristics of fast curing speed, high efficiency, low energy consumption, environmental friendliness, less solvent emission and wide applicability, which meets the "5E" principle and is a very green new technology. Therefore, photocuring has been widely used in the fields of coatings, inks and adhesives.

[0003] Ultraviolet photocuring has been widely used in the preparation of transparent coatings, but the problem of pollution of transparent coatings by fingerprints and other stains cannot be ignored. For the preparation of coating surfaces with special wetting behavior (hydrophobicity, superhydrophobicity, etc.), it is very important to reduce the surface energy and increase the surface roughness. In this case, fluorinated compounds are widely used to manufacture special wetting behavior coatings due to their unique properties such as low surface energy, high chemical stability and hydrophobicity. However, most fluorinated compounds not only have high cost, but also have persistence and bioaccumulation in nature, which means they are not easily degraded in the environment and can accumulate in living organisms, including humans. In addition, the process of using fluorinated compounds to manufacture coatings produces greenhouse gases and other pollutants, leading to climate change and air pollution. Therefore, it is of great significance to use fluorine-free materials to manufacture coatings with special wetting behavior to meet environmental protection requirements. SUMMARY

[0004] The purpose of the present application is to provide a plant oil modified fluorine-free anti-fingerprint transparent coating material and a preparation method and application thereof. The prepared coating is fluorine-free, transparent, has excellent hydrophobic effect and anti-fingerprint performance.

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

[0006] The present application provides a preparation method of a plant oil modified fluorine-free anti-fingerprint transparent coating material, comprising the following steps:

[0007] Mixing the organosilicon modified polyurethane acrylate prepolymer, plant oil, photoinitiator, hydrophobic nanoparticles and organic solvent to obtain a mixed coating;

[0008] Surface treating the substrate with a silane coupling agent solution to obtain a pretreated substrate;

[0009] The mixed coating is applied to the pretreated substrate and is subjected to ultraviolet curing to obtain a plant oil modified fluorine-free anti-fingerprint transparent coating material.

[0010] Preferably, the preparation method of the organic silicon modified polyurethane acrylate prepolymer comprises the following steps:

[0011] Under the protection of nitrogen, the both end hydroxyl polydimethylsiloxane and diisocyanate are mixed to perform a first reaction to obtain an intermediate;

[0012] The intermediate is mixed with a hydroxyl acrylate monomer and an organic tin catalyst to perform a second reaction to obtain the organic silicon modified polyurethane acrylate prepolymer.

[0013] Preferably, the diisocyanate comprises at least one of isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hexamethylene diisocyanate and lysine diisocyanate; the hydroxyl acrylate monomer comprises at least one of beta-hydroxyethyl acrylate, beta-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, beta-hydroxyethyl methacrylate, beta-hydroxypropyl methacrylate and pentaerythritol triacrylate; and the organic tin catalyst comprises at least one of dibutyl tin dilaurate, stannous octoate and dibutyl tin diacetate.

[0014] Preferably, the temperature of the first reaction is 60-80℃ and the time is 2-5h; and the temperature of the second reaction is 60-80℃ and the time is 2-4h.

[0015] Preferably, the plant oil comprises one of tung oil, castor oil, flax oil, rubber seed oil, rapeseed oil, dogwood seed oil, sunflower seed oil, cottonseed oil, soybean oil and corn oil; and the mass of the plant oil is 1-20% of the total mass of the organic silicon modified polyurethane acrylate prepolymer and the plant oil.

[0016] Preferably, the photoinitiator comprises at least one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl phosphonate ethyl ester and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide; and the mass of the photoinitiator is 0.1-5% of the total mass of the organic silicon modified polyurethane acrylate prepolymer and the plant oil.

[0017] Preferably, the organic solvent comprises at least one of acetone, 2-butanone, tetrahydrofuran, ethyl acetate, butyl acetate and isopropyl acetate; the mass of the organic solvent is 2-8 times the total mass of the silicone-modified polyurethane acrylate prepolymer and the vegetable oil.

[0018] Preferably, the hydrophobic nanoparticles comprise at least one of hydrophobic nanosilica, zinc oxide and titanium dioxide; the mass of the hydrophobic nanoparticles is 1-20% of the total mass of the silicone-modified polyurethane acrylate prepolymer and the vegetable oil.

[0019] The present application provides a vegetable oil modified fluorine-free anti-fingerprint transparent coating material prepared by the preparation method.

[0020] The present application provides an application of the vegetable oil modified fluorine-free anti-fingerprint transparent coating material in anti-fingerprint materials.

[0021] The vegetable oil modified fluorine-free anti-fingerprint transparent coating material provided by the present application is compounded by a silicone-modified polyurethane acrylate prepolymer, a vegetable oil, a photoinitiator, an organic solvent and hydrophobic nanoparticles, and is formed by ultraviolet curing. The silicone-modified polymer coating prepared by the silicone-modified polyurethane acrylate prepolymer itself has transparency, low surface energy, and the introduced vegetable oil and hydrophobic nanoparticles can improve the surface roughness, so that the coating material has excellent hydrophobic effect and excellent anti-fingerprint performance. The results of the examples show that it has a water contact angle of more than 100°, a light transmittance of more than 80%, and an anti-fingerprint performance of removing fingerprint marks by wiping with a paper towel for 3 times or less.

[0022] The present application introduces a polydimethylsiloxane component into the structure of the polymer by a chemical method, which is more economical and environmentally friendly. The transparent coating material prepared by the present application is a silicone-modified polymer coating, which is fluorine-free, pollution-free and non-toxic, has no biological accumulation, and is environmentally friendly. Under ultraviolet light irradiation, it can be quickly photocured to reach the surface dry state, improving the production efficiency.

[0023] The coating of the present application uses vegetable oil as raw material, has the advantages of low cost, high usability, low toxicity, low viscosity at room temperature, etc., can be extracted in large quantities from nature, has a wide source of monomers, does not contain fluorine components, reduces the harmful effects of existing fluorine-containing transparent coatings on nature, and the preparation method used is easy to operate and simple in process, uses ultraviolet curing, and the preparation process and the obtained coating product are more green and environmentally friendly. DETAILED DESCRIPTION

[0024] The present application provides a preparation method of a vegetable oil modified fluorine-free anti-fingerprint transparent coating material, comprising the following steps:

[0025] Mixing the silicone-modified polyurethane acrylate prepolymer, vegetable oil, photoinitiator, hydrophobic nanoparticles and organic solvent to obtain a mixed coating;

[0026] Carrying out surface treatment on the substrate by using a silane coupling agent solution to obtain a pretreated substrate;

[0027] Coating the mixed coating on the pretreated substrate and carrying out ultraviolet curing to obtain a vegetable oil-modified fluorine-free anti-fingerprint transparent coating material.

[0028] In the present application, the raw materials used are all commercially available products well known in the art, unless otherwise specified.

[0029] The present application mixes the silicone-modified polyurethane acrylate prepolymer, vegetable oil, photoinitiator, hydrophobic nanoparticles and organic solvent to obtain a mixed coating.

[0030] In the present application, the preparation method of the silicone-modified polyurethane acrylate prepolymer preferably comprises the following steps:

[0031] Mixing the dihydroxy-terminated polydimethylsiloxane and diisocyanate under nitrogen protection to carry out a first reaction to obtain an intermediate;

[0032] Mixing the intermediate with hydroxy acrylate monomer and organotin catalyst to carry out a second reaction to obtain the silicone-modified polyurethane acrylate prepolymer.

[0033] In the present application, the diisocyanate preferably comprises at least one of isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hexamethylene diisocyanate and lysine diisocyanate; when the diisocyanate is two or more of the above, the present application does not have special limitations on the ratio of different types of diisocyanate, which can be adjusted according to actual needs.

[0034] In the present application, the molar ratio of the dihydroxy-terminated polydimethylsiloxane to diisocyanate is preferably 1:2; the temperature of the first reaction is preferably 60-80℃, more preferably 70-80℃; the time is preferably 2-5h, more preferably 3h, and the stirring speed is preferably 200-400rpm, more preferably 300rpm.

[0035] In the present application, the hydroxy acrylate monomer preferably includes at least one of β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl methacrylate and pentaerythritol triacrylate; and the organic tin catalyst preferably includes at least one of dibutyl tin dilaurate, stannous octoate and dibutyl tin diacetate. When two or more of the above are used as the hydroxy acrylate monomer or the organic tin catalyst, the present application does not have a special limitation on the ratio of different kinds of agents, which can be adjusted according to actual needs.

[0036] In the present application, the molar ratio of the diisocyanate to the hydroxy acrylate monomer is preferably 1:1, and the mass of the organic tin catalyst is preferably 0.1-2% of the total mass of the second reaction system, more preferably 0.2-0.3%.

[0037] In the present application, the temperature of the second reaction is preferably 60-80°C, and the time is preferably 2-4h, more preferably 3h.

[0038] In the present application, the hydroxy acrylate monomer preferably includes at least one of β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl methacrylate and pentaerythritol triacrylate; and the organic tin catalyst preferably includes at least one of dibutyl tin dilaurate, stannous octoate and dibutyl tin diacetate. When two or more of the above are used as the hydroxy acrylate monomer or the organic tin catalyst, the present application does not have a special limitation on the ratio of different kinds of agents, which can be adjusted according to actual needs.

[0039] In the present application, the plant oil preferably includes one of tung oil, castor oil, flax oil, rubber seed oil, rapeseed oil, alder seed oil, sunflower seed oil, cottonseed oil, soybean oil and corn oil; when two or more of the above are used as the plant oil, the present application does not have a special limitation on the ratio of different kinds of plant oils, which can be adjusted according to actual needs; and the mass of the plant oil is preferably 1-20% of the total mass of the silicone-modified polyurethane acrylate prepolymer and the plant oil, more preferably 10-20%.

[0040] In the present application, the photoinitiator preferably comprises at least one of 2-hydroxy-2-methyl-1-phenylpropanone (photoinitiator 1173), 1-hydroxycyclohexyl phenyl ketone (photoinitiator 184), 2,2-dimethoxy-2-phenylacetophenone (photoinitiator 651), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone (photoinitiator 369), 2-isopropylthioxanthone (photoinitiator ITX), 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide (photoinitiator TPO), 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester (photoinitiator TPO-L), phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide (photoinitiator 819); when the photoinitiator is two or more of the above, the present application does not have special limitation on the ratio of different kinds of photoinitiators, which can be adjusted according to actual needs; the mass of the photoinitiator is preferably 0.1-5% of the total mass of the organosilicon-modified polyurethane acrylate prepolymer and the vegetable oil, and more preferably 2-4%.

[0041] In the present application, the hydrophobic nanoparticles preferably comprise at least one of hydrophobic nanosilica, zinc oxide and titanium dioxide; when the hydrophobic nanoparticles are two or more of the above, the present application does not have special limitation on the ratio of different kinds of hydrophobic nanoparticles, which can be adjusted according to actual needs; the present application does not have special limitation on the specifications of the hydrophobic nanoparticles, and the corresponding commercially available products known in the art can be used; the mass of the hydrophobic nanoparticles is preferably 1-20% of the total mass of the organosilicon-modified polyurethane acrylate prepolymer and the vegetable oil, and more preferably 10-15%.

[0042] In the present application, the organic solvent preferably comprises at least one of acetone, 2-butanone, tetrahydrofuran, ethyl acetate, butyl acetate and isopropyl acetate; when the organic solvent is two or more of the above, the present application does not have special limitation on the ratio of different kinds of organic solvents, which can be adjusted according to actual needs; the mass of the organic solvent is preferably 2-8 times, and more preferably 4-6 times, of the total mass of the organosilicon-modified polyurethane acrylate prepolymer and the vegetable oil.

[0043] In the present application, the surface of the substrate is treated with a silane coupling agent solution to obtain a pretreated substrate.

[0044] In the present application, the mass concentration of the silane coupling agent solution is preferably 0.5-5%, more preferably 1-4%, and further preferably 2-3%, the silane coupling agent in the silane coupling agent solution preferably includes one or more of γ-aminopropyl triethoxysilane, γ-glycidyl ether propyl trimethoxysilane, γ-methacryloyloxy propyl trimethoxysilane, γ-mercaptopropyl triethoxysilane, γ-mercaptopropyl trimethoxysilane, vinyl trimethoxysilane, and vinyl triethoxysilane, and the solvent used in the silane coupling agent solution is preferably at least one of water, methanol, and ethanol; when the silane coupling agent or the above-mentioned solvent is two or more of the above, the present application does not have special limitations on the ratio of different kinds of agents, which can be adjusted according to actual needs. The present application uses a silane coupling agent to enhance the adhesion between the coating and the substrate.

[0045] The present application does not have special limitations on the substrate, and the substrate commonly used in the present application for coating can be used; in the embodiments of the present application, the substrate is specifically a glass slide.

[0046] In the present application, the surface treatment is preferably dipping, and the present application does not have special limitations on the conditions of the dipping, which can be performed according to the processes commonly known in the art; after the surface treatment is completed, the obtained substrate is preferably dried, the drying temperature is preferably 110-120°C, and the time is preferably 10-20 min.

[0047] The present application coats the mixed coating on the pretreated substrate, performs ultraviolet curing, and obtains a plant oil modified fluorine-free anti-fingerprint transparent coating material.

[0048] In the present application, the coating is preferably spraying; 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 pretreated substrate is preferably 0.001-0.005 g / cm 2 .

[0049] In the present application, the ultraviolet curing is preferably performed under a UV-LED lamp, and the curing time of the ultraviolet curing is preferably 30-300 s, more preferably 60-200 s, and further preferably 60-90 s.

[0050] In the process of ultraviolet curing, the photoinitiator absorbs ultraviolet light and is converted into a free radical, which initiates the crosslinking of the prepolymer and the double bond in the plant oil, so as to cure the coating.

[0051] The present application provides a plant oil modified fluorine-free anti-fingerprint transparent coating material prepared by the preparation method of the above technical solution.

[0052] The application provides application of the plant oil modified fluorine-free anti-fingerprint transparent coating material in an anti-fingerprint material.

[0053] The technical solutions provided by the application are described in detail below in combination with examples, but they should not be understood as limitations to the protection scope of the application.

[0054] Example 1

[0055] (1) The surface of a glass slide was cleaned, and the surface of the substrate was immersed in a 2% mass concentration γ-mercaptopropyltrimethoxysilane ethanol solution, and then the substrate was dried at 110 ℃ for 10 min to obtain a pretreated substrate;

[0056] (2) 0.1 g of flax oil, 0.04 g of a photoinitiator 651, 4 g of butyl acetate and 0.1 g of hydrophobic nano-silicon dioxide particles (with a particle size of 20 nm) were added to 0.9 g of a silicone-modified polyurethane acrylate prepolymer, and then the mixture was stirred uniformly to obtain a mixed coating;

[0057] (3) The mixed coating was sprayed on the surface-treated glass slide at a pressure of 0.25 MPa;

[0058] (4) The substrate with the coating was placed under a UV-LED lamp for ultraviolet irradiation for 90 s to obtain a transparent coating.

[0059] The preparation process of the silicone-modified polyurethane acrylate prepolymer includes the following steps:

[0060] Under the protection of nitrogen, double-end hydroxyl polydimethylsiloxane and hexamethylene diisocyanate were sequentially added to a three-necked flask at a molar ratio of 1:2, mechanical stirring was performed at a speed of 300 rpm, and reaction was performed at 80 ℃ for 3 h; then methacrylic acid-β-hydroxypropyl ester in an equal molar amount of the hexamethylene diisocyanate and dibutyl tin diacetate accounting for 0.3% of the total mass of the reaction system were added dropwise, and reaction was performed at 80 ℃ for 3 h to obtain the silicone-modified polyurethane acrylate prepolymer, which has the following structure:

[0061]

[0062] R is

[0063] R1 is R2 is

[0064] Example 2

[0065] (1) The surface of the glass slide was cleaned, and the surface of the substrate was immersed in an ethanol solution of vinyltriethoxysilane with a mass concentration of 4%, and then dried at 110°C for 10 min to obtain a pretreated substrate;

[0066] (2) 0.1 g of linseed oil, 0.04 g of photoinitiator 651, 4 g of butyl acetate, and 0.2 g of hydrophobic nano-silica particles (particle size of 20 nm) were added to 0.9 g of silicone-modified polyurethane acrylate prepolymer, and then stirred uniformly to obtain a mixed coating;

[0067] (3) The mixed coating was sprayed on the surface-treated glass slide at a pressure of 0.2 MPa;

[0068] (4) The substrate with the coating was placed under a UV-LED lamp for UV irradiation for 90 s to obtain a transparent coating.

[0069] The preparation process of the silicone-modified polyurethane acrylate prepolymer includes the following steps:

[0070] Under nitrogen protection, the double-end hydroxyl polydimethylsiloxane and hexamethylene diisocyanate were added to a three-necked flask in a molar ratio of 1:2, and mechanically stirred at a speed of 300 rpm. The reaction was carried out at 80°C for 3 h, then an equal molar amount of methyl methacrylate-β-hydroxypropyl ester and 0.3% of dibutyl tin diacetate based on the total mass of the reaction system were added dropwise, and the reaction was carried out at 80°C for 3 h to obtain the silicone-modified polyurethane acrylate prepolymer, which has the following structure:

[0071]

[0072] wherein R is

[0073] R1 is R2 is

[0074] Example 3

[0075] (1) The surface of the glass slide was cleaned, and the surface of the substrate was immersed in an ethanol solution of γ-mercaptopropyl triethoxysilane with a mass concentration of 3%, and then dried at 110°C for 10 min to obtain a pretreated substrate;

[0076] (2) 0.2 g of tung oil, 0.04 g of photoinitiator TPO-L, 4 g of butyl acetate, and 0.1 g of hydrophobic nano-silica particles (particle size of 20 nm) were added to 0.8 g of silicone-modified polyurethane acrylate prepolymer, and then stirred uniformly to obtain a mixed coating;

[0077] (3) The mixed paint is sprayed on the surface treated glass slide at a pressure of 0.25 MPa;

[0078] (4) The substrate with the coating is placed under a UV-LED lamp for ultraviolet irradiation for 60 s to obtain a transparent coating.

[0079] The preparation process of the organosilicon modified polyurethane acrylate prepolymer includes the following steps:

[0080] Under nitrogen protection, the both-end hydroxyl polydimethylsiloxane and isophorone diisocyanate are sequentially added to a three-necked flask at a molar ratio of 1:2, mechanical stirring speed is 300 rpm, reaction is carried out at 80℃ for 3 h, then equimolar amount of pentaerythritol triacrylate and 0.2% of dibutyltin dilaurate in total mass of the reaction system are added dropwise, reaction is carried out at 80℃ for 3 h to obtain the organosilicon modified polyurethane acrylate prepolymer, the structure of which is as follows:

[0081]

[0082] Wherein, R is

[0083] R1 is R2 is

[0084] Example 4

[0085] (1) The surface of the glass slide is cleaned, the substrate surface is immersed in a 3% mass concentration of γ-mercaptopropyl triethoxysilane ethanol solution, and the pretreated substrate is obtained after drying at 110℃ for 10 min;

[0086] (2) 0.2 g of tung oil, 0.04 g of photoinitiator TPO-L, 4 g of butyl acetate and 0.2 g of hydrophobic nano-silicon dioxide particles (particle size is 20 nm) are added to 0.8 g of organosilicon modified polyurethane acrylate prepolymer, and the mixed paint is obtained after stirring uniformly;

[0087] (3) The mixed paint is sprayed on the surface treated glass slide at a pressure of 0.2 MPa;

[0088] (4) The substrate with the coating is placed under a UV-LED lamp for ultraviolet irradiation for 60 s to obtain a transparent coating.

[0089] The preparation process of the organosilicon modified polyurethane acrylate prepolymer includes the following steps:

[0090] Under the protection of nitrogen, double-end hydroxyl polydimethylsiloxane, isophorone diisocyanate were added into a three-necked flask in a molar ratio of 1:2, mechanical stirring speed was 300 rpm, reaction was carried out at 80℃ for 3h, then equimolar amount of pentaerythritol triacrylate and 0.2% of dibutyl tin dilaurate in total mass of the reaction system were added dropwise, reaction was carried out at 80℃ for 3h, to obtain a silicone-modified polyurethane acrylate prepolymer, the structure of which is as follows:

[0091] wherein R is

[0092]

[0093] R1 is R2 is

[0094] Example 5

[0095] (1) The surface of the glass slide was cleaned, and the surface of the substrate was immersed in a 2% mass concentration of γ-methacryloxypropyltrimethoxysilane ethanol solution, and then dried at 110℃ for 10 min to obtain a pretreated substrate;

[0096] (2) 0.1g of linseed oil, 0.04g of photoinitiator 819, 4g of butyl acetate and 0.1g of hydrophobic nano zinc oxide particles (particle size of 30nm) were added to 0.9g of the silicone-modified polyurethane acrylate prepolymer, and stirred uniformly to obtain a mixed coating;

[0097] (3) The mixed coating was sprayed on the surface-treated glass slide at a pressure of 0.25MPa;

[0098] (4) The substrate with the coating was placed under a UV-LED lamp for ultraviolet irradiation for 60s to obtain a transparent coating.

[0099] The preparation process of the silicone-modified polyurethane acrylate prepolymer includes the following steps:

[0100] Under the protection of nitrogen, double-end hydroxyl polydimethylsiloxane, isophorone diisocyanate were added into a three-necked flask in a molar ratio of 1:2, mechanical stirring speed was 300 rpm, reaction was carried out at 80℃ for 3h, then equimolar amount of pentaerythritol triacrylate and 0.2% of dibutyl tin dilaurate in total mass of the reaction system were added dropwise, reaction was carried out at 80℃ for 3h, to obtain a silicone-modified polyurethane acrylate prepolymer, the structure of which is as follows:

[0101]

[0102] wherein R is

[0103] R1is R2is

[0104] Comparative Example 1

[0105] (1) The surface of the glass slide was cleaned, and the surface of the substrate was immersed in a 2% mass concentration of γ-mercaptopropyl trimethoxysilane ethanol solution, and then dried at 110°C for 10 min to obtain a pretreated substrate;

[0106] (2) 0.04 g of photoinitiator 651 and 4 g of ethyl acetate were added to 1 g of silicone-modified polyurethane acrylate prepolymer, and then stirred uniformly to obtain a mixed coating;

[0107] (3) The mixed coating was sprayed on the surface-treated glass slide at a pressure of 0.3 MPa;

[0108] (4) The substrate with the coating was placed under a UV-LED lamp for UV irradiation for 90 s to obtain a transparent coating.

[0109] The preparation process of the silicone-modified polyurethane acrylate prepolymer includes the following steps:

[0110] Under the protection of nitrogen, the double-end hydroxyl polydimethylsiloxane and hexamethylene diisocyanate were added to a three-necked flask in a molar ratio of 1:2, and mechanically stirred at a speed of 300 rpm. The reaction was carried out at 80°C for 3 h, then an equal molar amount of β-hydroxyethyl methacrylate and 0.3% of dibutyl tin diacetate based on the total mass of the reaction system were added dropwise, and the reaction was carried out at 80°C for 3 h to obtain a silicone-modified polyurethane acrylate prepolymer, the structure of which is as follows:

[0111]

[0112] R is

[0113] R1is R2is

[0114] Comparative Example 2

[0115] (1) The surface of the glass slide was cleaned, and the surface of the substrate was immersed in a 2% mass concentration of γ-mercaptopropyl trimethoxysilane ethanol solution, and then dried at 110°C for 10 min to obtain a pretreated substrate;

[0116] (2) 0.1 g of flax oil, 0.04 g of photoinitiator 651 and 4 g of ethyl acetate were added to 0.9 g of silicone-modified polyurethane acrylate prepolymer, and then stirred uniformly to obtain a mixed coating;

[0117] (3) The mixed paint is sprayed on the surface treated glass slide at a pressure of 0.3 MPa;

[0118] (4) The substrate with coating is placed under UV-LED lamp for UV irradiation for 90 s to obtain a transparent coating.

[0119] The preparation process of the organosilicon modified polyurethane acrylate prepolymer includes the following steps:

[0120] Under nitrogen protection, double-end hydroxyl polydimethylsiloxane and hexamethylene diisocyanate are added into a three-necked flask in a molar ratio of 1:2, mechanical stirring speed is 300 rpm, reaction is carried out at 80℃ for 3 h, then methacrylic acid-β-hydroxyethyl ester in an equal molar amount of hexamethylene diisocyanate and 0.3% of dibutyl tin diacetate in total mass of the reaction system are added dropwise, reaction is carried out at 80℃ for 3 h to obtain an organosilicon modified polyurethane acrylate prepolymer, the structure of which is as follows:

[0121]

[0122] In the formula, R is

[0123] R1 is R2 is

[0124] Comparative Example 3

[0125] (1) The surface of the glass slide is cleaned, and the surface of the substrate is immersed in a 3% mass concentration γ-mercaptopropyl triethoxysilane ethanol solution, and then dried at 110℃ for 10 min to obtain a pretreated substrate;

[0126] (2) 0.2 g of tung oil, 0.04 g of photoinitiator TPO-L and 4 g of ethyl acetate are added to 0.8 g of organosilicon modified polyurethane acrylate prepolymer, and then stirred uniformly to obtain a mixed paint;

[0127] (3) The mixed paint is sprayed on the surface treated glass slide at a pressure of 0.3 MPa;

[0128] (4) The substrate with coating is placed under UV-LED lamp for UV irradiation for 60 s to obtain a transparent coating.

[0129] The preparation process of the organosilicon modified polyurethane acrylate prepolymer includes the following steps:

[0130] Under nitrogen protection, double-end hydroxyl polydimethylsiloxane, isophorone diisocyanate were added into a three-necked flask in a molar ratio of 1:2, mechanical stirring speed was 300 rpm, reaction was carried out at 80℃ for 3h, then equimolar amount of pentaerythritol triacrylate and 0.2% of dibutyl tin dilaurate in total mass of the reaction system were added dropwise, reaction was carried out at 80℃ for 3h, to obtain a silicone-modified polyurethane acrylate prepolymer, the structure of which is as follows:

[0131] wherein R is

[0132]

[0133] R1 is R2 is

[0134] Performance test

[0135] 1) Contact angle test: the contact angle of the coating prepared in Examples 1-5 and Comparative Examples 1-3 was measured using a standard contact angle measuring instrument, and the results are shown in Table 1.

[0136] Table 1 Contact angle of the coating prepared in Examples 1-5 and Comparative Examples 1-3

[0137]

[0138] As can be seen from Table 1, after adding vegetable oil in the prepolymer, the contact angle of the coating is slightly improved; after adding vegetable oil and hydrophobic nanoparticles in the prepolymer, the water contact angle of the coating is greatly improved, which can be increased to about 110°.

[0139] 2) Fingerprint resistance test: the artificial fingerprint fluid is composed of 95% artificial sweat and 5% artificial sebum. The artificial sweat is 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, and the artificial sebum is composed of oleic acid (2%), stearic acid (2%), and squalene (1%). After mixing the artificial sweat and artificial sebum, a small amount of non-ionic surfactant (Triton X-100, added amount 2 μL / g of the mixture) is added to overcome the natural immiscibility between sweat and sebum. First, clean the fingers with alcohol, then immerse the fingers in the artificial fingerprint fluid, then touch the coating surface to form a fingerprint, then wipe with a paper towel under a load of 500g at a speed of 3cm / s, and record the number of wipes that can make the fingerprint disappear. The results are shown in Table 2.

[0140] Table 2 Fingerprint resistance of the coating prepared in Examples 1-5 and Comparative Examples 1-3

[0141]

[0142] From Table 2, it can be seen that the anti-fingerprint property of the coating is improved after adding vegetable oil and hydrophobic nanoparticles.

[0143] 3) Light transmittance test: the light transmittance of different coatings was measured using an ultraviolet-visible spectrophotometer, and the transmittance at 550 nm was used as the standard. The results are shown in Table 3.

[0144] Table 3 Light transmittance of the coatings prepared in Examples 1-5 and Comparative Examples 1-3

[0145]

[0146] From Table 3, it can be seen that the addition of vegetable oil and hydrophobic nanoparticles causes a slight decrease in transparency, but when the amount of vegetable oil is 20% or less of the total mass of the silicone-modified polyurethane acrylate prepolymer and vegetable oil, and the amount of hydrophobic nanoparticles is 20% or less of the total mass of the prepolymer and vegetable oil, the light transmittance of the coating at 550 nm is still above 80%.

[0147] The above description is only preferred embodiments of the present application, and it should be pointed out 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 also be considered as the protection scope of the present application.

Claims

1. A method for preparing a vegetable oil-modified fluorine-free anti-fingerprint transparent coating material, characterized in that, Includes the following steps: A mixed coating is obtained by mixing silicone-modified polyurethane acrylate prepolymer, vegetable oil, photoinitiator, hydrophobic nanoparticles and organic solvent; The substrate was surface-treated with a silane coupling agent solution to obtain a pretreated substrate; The mixed coating is applied to the pretreated substrate and cured under ultraviolet light to obtain a vegetable oil-modified fluorine-free anti-fingerprint transparent coating material. The preparation method of the organosilicon-modified polyurethane acrylate prepolymer includes the following steps: Under nitrogen protection, hydroxyl-terminated polydimethylsiloxane and diisocyanate were mixed and subjected to a first reaction to obtain an intermediate. The intermediate was mixed with hydroxy acrylate monomer and organotin catalyst to carry out a second reaction, thereby obtaining organosilicon-modified polyurethane acrylate prepolymer. The vegetable oil includes one of tung oil, linseed oil, rubber seed oil, rapeseed oil, bark tree seed oil, sunflower seed oil, cottonseed oil, soybean oil, and corn oil; the mass of the vegetable oil is 1-20% of the total mass of the organosilicon-modified polyurethane acrylate prepolymer and the vegetable oil. The hydrophobic nanoparticles include at least one of hydrophobic nano-silica, zinc oxide, and titanium dioxide; the mass of the hydrophobic nanoparticles is 1 to 20% of the total mass of the organosilicon-modified polyurethane acrylate prepolymer and vegetable oil.

2. The preparation method according to claim 1, characterized in that, The diisocyanate includes at least one selected from isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate; the hydroxy acrylate monomer includes at least one selected from β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl methacrylate, and pentaerythritol triacrylate. The organotin catalyst includes at least one of dibutyltin dilaurate, stannous octoate, and dibutyltin diacetate.

3. The preparation method according to claim 1 or 2, characterized in that, The temperature of the first reaction is 60–80°C and the time is 2–5 h; the temperature of the second reaction is 60–80°C and the time is 2–4 h.

4. The preparation method according to claim 1, characterized in that, The photoinitiator includes at least one selected from 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; The photoinitiator is 0.1-5% of the total mass of the silicone-modified polyurethane acrylate prepolymer and vegetable oil.

5. The preparation method according to claim 1, characterized in that, The organic solvent includes at least one of acetone, 2-butanone, tetrahydrofuran, ethyl acetate, butyl acetate, and isopropyl acetate; the mass of the organic solvent is 2 to 8 times the total mass of the organosilicon-modified polyurethane acrylate prepolymer and the vegetable oil.

6. The vegetable oil-modified fluorine-free anti-fingerprint transparent coating material prepared by the preparation method according to any one of claims 1 to 5.

7. The application of the vegetable oil-modified fluorine-free anti-fingerprint transparent coating material according to claim 6 in anti-fingerprint materials.

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