Tung oil derivative composite fluoride-free anti-fingerprint transparent coating material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of anti-fingerprint coating materials, and provides a tung oil derivative composite fluoride-free anti-fingerprint transparent coating material as well as a preparation method and application thereof. The preparation method comprises the following steps: mixing a polydimethylsiloxane modified polyurethane acrylate prepolymer, a tung oil-based photoactive monomer, a photoinitiator and an organic solvent, coating a pretreated base material with the mixed coating, and carrying out ultraviolet curing to obtain the tung oil derivative composite fluoride-free fingerprint-resistant transparent coating material. The coating material disclosed by the invention has an excellent hydrophobic effect and excellent fingerprint resistance; the tung oil-based photoactive monomer can increase the content of bio-based substances in the coating and improve the green environmental protection property of the coating. The transparent coating provided by the invention has a water contact angle close to 110 degrees, light transmittance of 85% or more, and fingerprint resistance that fingerprints can be removed only by wiping the transparent coating with tissues for 4 times or less.

Description

Technical Field

[0001] The invention relates to the technical field of anti-fingerprint coating materials, and in particular to a tung oil derivative composite fluorine-free anti-fingerprint transparent coating material and a preparation method and application thereof. Background Art

[0002] Photocuring technology is a very important polymerization method that uses light to cause monomers or resins to undergo cross-linking reactions. Compared with traditional thermal curing, UV curing technology has the characteristics of fast curing speed, high efficiency, low energy consumption, environmental friendliness, low solvent emissions, and wide applicability. It complies with the "5E" principle and is a new green technology. Therefore, photocuring has been widely used in the fields of coatings, inks, adhesives, etc. However, the components in the photocuring system are usually derived from petrochemical products and are highly dependent on non-renewable resources. Therefore, the use of bio-based substances to prepare photoactive materials is in line with the current requirements for building an environmentally friendly society.

[0003] UV curing has been widely used to prepare clear coatings, but the problem that clear coatings are easily contaminated by stains such as fingerprints cannot be ignored. For the preparation of coating surfaces with special wetting behaviors (hydrophobicity, superhydrophobicity, etc.), reducing surface energy and increasing surface roughness are very important. In this context, fluorinated compounds are widely used to make special wetting behavior coatings due to their unique properties, such as low surface energy, high chemical stability, and hydrophobicity. However, most fluorinated compounds are not only costly, but also persistent and bioaccumulative in nature, which means that they are not easily degraded in the environment and can accumulate in organisms, including humans. In addition, the process of using fluorinated compounds to make coatings produces greenhouse gases and other pollutants, which contribute to climate change and air pollution.

[0004] Therefore, it is of great significance to use fluorine-free materials and bio-based photoactive monomers to manufacture coating materials with special wetting behaviors to meet environmental protection requirements. Summary of the invention

[0005] The purpose of the present invention is to provide a tung oil derivative composite fluorine-free anti-fingerprint transparent coating material and a preparation method and application thereof in view of the deficiencies in the prior art.

[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 tung oil derivative composite fluorine-free anti-fingerprint transparent coating material, comprising the following steps:

[0008] 1) mixing a polydimethylsiloxane-modified polyurethane acrylate prepolymer, a tung oil-based photoactive monomer, a photoinitiator and an organic solvent to obtain a mixed coating;

[0009] The substrate is surface treated by using a silane coupling agent solution to obtain a pretreated substrate;

[0010] 2) applying the mixed coating to the pretreated substrate and performing UV curing to obtain a tung oil derivative composite fluorine-free anti-fingerprint transparent coating material;

[0011] The mass of the tung oil-based photoactive monomer is 10 to 50% of the total mass of the polydimethylsiloxane-modified polyurethane acrylate prepolymer and the tung oil-based photoactive monomer;

[0012] The preparation method of the tung oil-based photoactive monomer comprises the following steps:

[0013] Conducting a first reaction of tung oil anhydride, hydroxy acrylate monomer, a first part of catalyst and a first part of polymerization inhibitor to obtain an intermediate;

[0014] The intermediate, glycidyl methacrylate, a second part of the catalyst and a second part of the polymerization inhibitor are subjected to a second reaction to obtain a tung oil-based photoactive monomer.

[0015] Preferably, the molar ratio of tung oil anhydride to hydroxy acrylate monomer is 1:2-4, and the molar ratio of tung oil anhydride to glycidyl methacrylate is 0.8-1.2:0.8-1.2.

[0016] Preferably, the mass of the first part of the catalyst is 0.8-1.2% of the total mass of tung oil anhydride and hydroxy acrylate monomers, and the mass of the first part of the inhibitor is 0.3-0.8% of the total mass of tung oil anhydride and hydroxy acrylate monomers; the mass of the second part of the catalyst is 0.8-1.2% of the mass of glycidyl methacrylate, and the mass of the second part of the inhibitor is 0.3-0.8% of the mass of glycidyl methacrylate.

[0017] Preferably, the hydroxyacrylate monomer includes one or more of β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl methacrylate and pentaerythritol triacrylate; the catalyst is N,N-dimethylethanolamine; and the inhibitor includes hydroquinone and / or 4-methoxyphenol.

[0018] Preferably, the temperature of the first reaction is 100-120° C., and the time of the first reaction is 3-5 hours; the temperature of the second reaction is 90-110° C., and the time of the second reaction is 3-4 hours.

[0019] Preferably, the method for preparing the polydimethylsiloxane-modified polyurethane acrylate prepolymer comprises the following steps:

[0020] Mixing aminopropyl di-terminated polydimethylsiloxane, butyl acetate and diisocyanate to carry out a first reaction to obtain an intermediate;

[0021] The intermediate, hydroxy acrylate monomer and organotin catalyst are mixed, and a second reaction is carried out under nitrogen protection to obtain a polydimethylsiloxane-modified polyurethane acrylate prepolymer;

[0022] The first reaction is carried out at room temperature for 1 to 3 hours; the second reaction is carried out at a temperature of 60 to 80° C. for 1 to 3 hours.

[0023] Preferably, the diisocyanate includes one or more of isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hexamethylene diisocyanate and lysine diisocyanate; the hydroxy acrylate monomer includes one or more of β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentahexaenoate, trimethylolpropane triacrylate and ditrimethylolpropane tetraacrylate; the organotin catalyst includes one or more of dibutyltin dilaurate, stannous octoate and dibutyltin diacetate.

[0024] Preferably, the photoinitiator comprises one or more of 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 mass of the photoinitiator is 15-25% of the total mass of the polydimethylsiloxane-modified polyurethane acrylate prepolymer and the tung oil-based photoactive monomer;

[0025] The organic solvent comprises one or more of acetone, 2-butanone, tetrahydrofuran, ethyl acetate, butyl acetate and isopropyl acetate; the mass of the organic solvent is 1 to 4 times the total mass of the polydimethylsiloxane-modified polyurethane acrylate prepolymer and the tung oil-based photoactive monomer.

[0026] The invention also provides a tung oil derivative composite fluorine-free anti-fingerprint transparent coating material prepared by the preparation method.

[0027] The present invention also provides application of the tung oil derivative composite fluorine-free anti-fingerprint transparent coating material in anti-fingerprint materials.

[0028] The beneficial effects of the present invention include the following:

[0029] 1) The tung oil derivative composite fluorine-free anti-fingerprint transparent coating material provided by the present invention is compounded with polydimethylsiloxane modified polyurethane acrylate prepolymer, tung oil-based photoactive monomer, photoinitiator and organic solvent, and is cured by ultraviolet light; the organosilicon-modified polymer coating prepared by polydimethylsiloxane modified polyurethane acrylate prepolymer itself has transparency and low surface energy, so the coating material has excellent hydrophobic effect and excellent anti-fingerprint performance; at the same time, the addition of tung oil-based photoactive monomer can increase the content of bio-based substances in the coating and improve the green environmental protection of the coating. The transparent coating of the present invention has a water contact angle of nearly 110°, a light transmittance of more than 85%, and an anti-fingerprint performance that can remove fingerprints by wiping with a paper towel less than 4 times.

[0030] 2) The transparent coating material of the present invention is an organosilicon modified polymer coating, which is fluorine-free, pollution-free, non-toxic, non-bioaccumulative, and environmentally friendly; the coating uses tung oil anhydride as a raw material, which is easy to obtain and low in cost. Tung oil anhydride can be synthesized by the Diels-Alder reaction of tung oil and maleic anhydride, and tung oil can be extracted in large quantities from plants in nature. The entire coating has no fluorine-containing components, thereby avoiding the harmful effects of existing fluorine-containing transparent coatings on nature and increasing the biomass content of the coating.

[0031] 3) The preparation method of the present invention is easy to operate, has a simple process, adopts ultraviolet light curing, can perform rapid light curing to reach a surface dry state, improves production efficiency, has lower energy consumption than traditional thermal curing, and the preparation process and the resulting coating product are more environmentally friendly. DETAILED DESCRIPTION

[0032] The present invention provides a method for preparing a tung oil derivative composite fluorine-free anti-fingerprint transparent coating material, comprising the following steps:

[0033] 1) mixing a polydimethylsiloxane-modified polyurethane acrylate prepolymer, a tung oil-based photoactive monomer, a photoinitiator and an organic solvent to obtain a mixed coating;

[0034] The substrate is surface treated by using a silane coupling agent solution to obtain a pretreated substrate;

[0035] 2) applying the mixed coating to the pretreated substrate and performing UV curing to obtain a tung oil derivative composite fluorine-free anti-fingerprint transparent coating material;

[0036] The mass of the tung oil-based photoactive monomer is 10 to 50% of the total mass of the polydimethylsiloxane-modified polyurethane acrylate prepolymer and the tung oil-based photoactive monomer;

[0037] The preparation method of the tung oil-based photoactive monomer comprises the following steps:

[0038] Conducting a first reaction of tung oil anhydride, hydroxy acrylate monomer, a first part of catalyst and a first part of polymerization inhibitor to obtain an intermediate;

[0039] The intermediate, glycidyl methacrylate, a second part of the catalyst and a second part of the polymerization inhibitor are subjected to a second reaction to obtain a tung oil-based photoactive monomer.

[0040] In the present invention, the mass of the tung oil-based photoactive monomer is preferably 20-40% of the total mass of the polydimethylsiloxane-modified polyurethane acrylate prepolymer and the tung oil-based photoactive monomer, and more preferably 30%.

[0041] In the present invention, the molar ratio of tung oil anhydride to hydroxy acrylate monomer is preferably 1:2-4, more preferably 1:2.5-3.5, and more preferably 1:3; the molar ratio of tung oil anhydride to glycidyl methacrylate is preferably 0.8-1.2:0.8-1.2, more preferably 0.9-1.1:0.9-1.1, and more preferably 1:1.

[0042] In the present invention, the mass of the first part of the catalyst is preferably 0.8-1.2% of the total mass of tung oil anhydride and hydroxy acrylate monomers, more preferably 0.9-1.1%, and more preferably 1.0%; the mass of the first part of the polymerization inhibitor is preferably 0.3-0.8% of the total mass of tung oil anhydride and hydroxy acrylate monomers, more preferably 0.4-0.6%, and more preferably 0.5%; the mass of the second part of the catalyst is preferably 0.8-1.2% of the mass of glycidyl methacrylate, more preferably 0.9-1.1%, and more preferably 1.0%, and the mass of the second part of the polymerization inhibitor is preferably 0.3-0.8% of the mass of glycidyl methacrylate, more preferably 0.4-0.6%, and more preferably 0.5%.

[0043] In the present invention, the hydroxy acrylate monomer preferably includes one or more of β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentahexaenoic acid ester, trimethylolpropane triacrylate and ditrimethylolpropane tetraacrylate; the catalyst is preferably N,N-dimethylethanolamine; and the inhibitor preferably includes hydroquinone and / or 4-methoxyphenol.

[0044] In the present invention, the temperature of the first reaction is preferably 100-120°C, more preferably 105-115°C, and more preferably 110°C; the time of the first reaction is preferably 3-5h, more preferably 3.5-4.5h, and more preferably 4h; the temperature of the second reaction is preferably 90-110°C, more preferably 95-105°C, and more preferably 100°C; the time of the second reaction is preferably 3-4h, and more preferably 3.5h.

[0045] In the method for preparing the tung oil-based photoactive monomer of the present invention, the first reaction and the second reaction are carried out under stirring conditions, and the stirring speed is preferably 200-400 rpm, more preferably 250-350 rpm, and more preferably 280-300 rpm.

[0046] In the present invention, the preparation method of the polydimethylsiloxane-modified polyurethane acrylate prepolymer comprises the following steps:

[0047] Mixing aminopropyl di-terminated polydimethylsiloxane, butyl acetate and diisocyanate to carry out a first reaction to obtain an intermediate;

[0048] The intermediate, hydroxy acrylate monomer and organotin catalyst are mixed, and a second reaction is carried out under nitrogen protection to obtain a polydimethylsiloxane-modified polyurethane acrylate prepolymer.

[0049] In the present invention, the first reaction is preferably carried out at room temperature, and the time of the first reaction is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and more preferably 2 hours; the temperature of the second reaction is preferably 60 to 80°C, more preferably 65 to 75°C, and more preferably 70°C; the time of the second reaction is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and more preferably 2 hours.

[0050] In the present invention, the diisocyanate preferably includes one or more of isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.

[0051] In the present invention, when there are two or more diisocyanates, there is no special limitation on the ratio of different types of diisocyanates, which can be adjusted according to actual needs.

[0052] In the present invention, aminopropyl diblocked polydimethylsiloxane, butyl acetate and diisocyanate are mixed, preferably aminopropyl diblocked polydimethylsiloxane is dissolved in butyl acetate, and then diisocyanate is added dropwise; the intermediate, hydroxy acrylate monomer and organotin catalyst are mixed, preferably hydroxy acrylate monomer and organotin catalyst are added dropwise to the intermediate.

[0053] In the present invention, the molar ratio of aminopropyl di-terminated polydimethylsiloxane to diisocyanate is preferably 1:1.5 to 2.5, and more preferably 1:2.

[0054] In the present invention, the hydroxyacrylate monomer preferably includes one or more of β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl methacrylate and pentaerythritol triacrylate.

[0055] In the present invention, the organotin catalyst preferably includes one or more of dibutyltin dilaurate, stannous octoate and dibutyltin diacetate.

[0056] In the present invention, when there are two or more hydroxy acrylate monomers or organotin catalysts, the present invention has no particular limitation on the ratio of different types of hydroxy acrylate monomers or organotin catalysts, and the ratio can be adjusted according to actual needs.

[0057] In the present invention, the molar ratio of the diisocyanate to the hydroxy acrylate monomer is preferably 1:1, and the mass of the organotin catalyst is preferably 0.1-2% of the total mass of the second reaction system, more preferably 0.2-1%, and more preferably 0.3-0.5%.

[0058] In the present invention, the photoinitiator preferably includes 2-hydroxy-2-methyl-1-phenylpropanone (photoinitiator 1173), 1-hydroxycyclohexylphenyl 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- One or more of diphenylphosphine oxide (photoinitiator TPO), ethyl 2,4,6-trimethylbenzoylphenylphosphonate (photoinitiator TPO-L) and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator 819); the mass of the photoinitiator is preferably 15-25% of the total mass of the polydimethylsiloxane-modified polyurethane acrylate prepolymer and the tung oil-based photoactive monomer, more preferably 18-22%, and more preferably 20%;

[0059] The organic solvent preferably includes one or more of acetone, 2-butanone, tetrahydrofuran, ethyl acetate, butyl acetate and isopropyl acetate; the mass of the organic solvent is preferably 1 to 4 times the total mass of the polydimethylsiloxane-modified polyurethane acrylate prepolymer and the tung oil-based photoactive monomer, and more preferably 2 to 3 times.

[0060] In the present invention, when there are two or more photoinitiators or organic solvents, the present invention has no special limitation on the ratio of different types of photoinitiators and organic solvents, and the ratio can be adjusted according to actual needs.

[0061] In the present invention, unless otherwise specified, the raw materials used are commercially available products well known in the art.

[0062] In the present invention, the mass concentration of the silane coupling agent solution is preferably 0.5-5%, more preferably 1-4%, and more preferably 2-3%. In the silane coupling agent solution, the silane coupling agent preferably includes one or more of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane, and the solvent used is preferably one or more of water, methanol and ethanol; when the silane coupling agent or the above-mentioned solvent is two or more, the present invention has no special limitation on the ratio of different types of silane coupling agents and solvents, which can be adjusted according to actual needs.

[0063] In the present invention, a silane coupling agent is used to enhance the adhesion between the coating and the substrate.

[0064] The present invention has no particular limitation on the substrate, and any coating substrate known in the present invention may be used, preferably a glass slide.

[0065] In the present invention, the surface treatment method is preferably impregnation. The present invention has no special limitation on the conditions of the impregnation, and the impregnation can be carried out according to the process well known in the art. After the surface treatment is completed, the obtained substrate is preferably dried. The drying temperature is preferably 110 to 120°C, more preferably 115°C, and the drying time is preferably 10 to 20 minutes, more preferably 15 minutes.

[0066] In the present invention, the coating method is preferably spraying; the spraying pressure is preferably 0.1 to 2 MPa, more preferably 0.2 to 1 MPa, and more preferably 0.25 to 0.3 MPa.

[0067] In the present invention, the coating amount of the mixed coating on the pre-treated substrate is preferably 0.001 to 0.005 g / cm 2 .

[0068] In the present invention, the ultraviolet light curing is preferably carried out under a UV-LED lamp, and the ultraviolet light curing time is preferably 2 to 5 minutes, and more preferably 3 to 4 minutes.

[0069] In the present invention, during the UV curing process, the photoinitiator absorbs UV light and is converted into free radicals, which initiate the cross-linking of the double bonds in the prepolymer and the tung oil-based photoactive monomer, thereby curing the coating.

[0070] The invention also provides a tung oil derivative composite fluorine-free anti-fingerprint transparent coating material prepared by the preparation method.

[0071] The present invention also provides application of the tung oil derivative composite fluorine-free anti-fingerprint transparent coating material in anti-fingerprint materials.

[0072] The present invention has no particular limitation on the application method, and the application can be carried out according to methods well known in the art.

[0073] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0074] Example 1

[0075] (1) Cleaning the surface of a glass slide, dipping the glass slide in an ethanol solution of γ-mercaptopropyltrimethoxysilane with a mass concentration of 2%, dipping for 10 minutes, and then drying at 110° C. for 10 minutes to obtain a pretreated glass slide;

[0076] (2) adding 0.1 g of tung oil-based photoactive monomer, 0.2 g of photoinitiator 651 and 2 g of butyl acetate to a solution containing 0.9 g of polydimethylsiloxane-modified polyurethane acrylate prepolymer, stirring evenly to obtain a mixed coating;

[0077] (3) The mixed coating was sprayed on the pretreated glass slide at a pressure of 0.25 MPa, with a spraying amount of 0.002 g / cm 2 ;

[0078] (4) The coated glass slide was placed under a UV-LED lamp for 3 min to obtain a transparent coating.

[0079] The preparation method of the polydimethylsiloxane modified polyurethane acrylate prepolymer is as follows: dissolving aminopropyl diblocked polydimethylsiloxane in an appropriate amount of butyl acetate to obtain a siloxane solution (solid content is 8%), adding a butyl acetate solution of hexamethylene diisocyanate (the solid content of the butyl acetate solution of hexamethylene diisocyanate is 10%, and the molar ratio of aminopropyl diblocked polydimethylsiloxane to hexamethylene diisocyanate is 1:2) dropwise (dropping rate is 2s / drop) to the siloxane solution, and after the dropwise addition is completed, reacting with magnetic stirring at a rate of 300rpm at room temperature for 2h, and then transferring the reaction solution to a three-necked flask, adding β-hydroxypropyl methacrylate in an equal molar amount to hexamethylene diisocyanate and dibutyltin diacetate accounting for 0.3% of the total mass of the reaction system, and reacting for 2h at 80°C under nitrogen protection to obtain a polydimethylsiloxane modified polyurethane acrylate prepolymer, the structural formula of which is as follows:

[0080]

[0081] Among them, R is R 1 for R 2 for n is 30.

[0082] The preparation method of the tung oil-based photoactive monomer is as follows: tung oil anhydride and β-hydroxypropyl methacrylate are added to a three-necked flask at a molar ratio of 1:3, 1% of N,N-dimethylethanolamine and 0.5% of 4-methoxyphenol are added to the total mass of the reaction system (the total mass of tung oil anhydride and β-hydroxypropyl methacrylate), the temperature is raised to 100°C, and the reaction is carried out at a speed of 280 rpm for 4 hours, and then the temperature is lowered to 60°C, and an equal molar amount of glycidyl methacrylate is added to the tung oil anhydride, and 1% of N,N-dimethylethanolamine and 0.5% of 4-methoxyphenol are added to the mass of glycidyl methacrylate, the temperature is raised to 100°C, and the reaction is carried out at a speed of 280 rpm for 4 hours to obtain a tung oil-based photoactive monomer, and the structural formula is as follows:

[0083]

[0084] Among them, R 3 for R 4 for

[0085] Example 2

[0086] (1) Cleaning the surface of a glass slide, dipping the glass slide in an ethanol solution of vinyltriethoxysilane having a mass concentration of 4%, dipping for 10 minutes, and then drying at 120° C. for 15 minutes to obtain a pretreated glass slide;

[0087] (2) adding 0.2 g of tung oil-based photoactive monomer, 0.2 g of photoinitiator 651 and 2 g of butyl acetate to a solution containing 0.8 g of polydimethylsiloxane-modified polyurethane acrylate prepolymer, stirring evenly to obtain a mixed coating;

[0088] (3) The mixed coating was sprayed on the pretreated glass slide at a pressure of 0.2 MPa, with a spraying amount of 0.002 g / cm 2 ;

[0089] (4) The coated glass slide was placed under a UV-LED lamp for 3 min to obtain a transparent coating.

[0090] The preparation method of the polydimethylsiloxane modified polyurethane acrylate prepolymer is as follows: dissolving aminopropyl diblocked polydimethylsiloxane in an appropriate amount of butyl acetate (solid content of 8%) to obtain a siloxane solution, adding a butyl acetate solution of hexamethylene diisocyanate (the solid content of the butyl acetate solution of hexamethylene diisocyanate is 10%, and the molar ratio of aminopropyl diblocked polydimethylsiloxane to hexamethylene diisocyanate is 1:2) dropwise (dropping rate of 3s / drop) to the siloxane solution, and after the dropwise addition is completed, reacting with magnetic stirring at a rate of 300rpm at room temperature for 2h, and then transferring the reaction solution to a three-necked flask, adding β-hydroxypropyl methacrylate in an equal molar amount to hexamethylene diisocyanate and dibutyltin diacetate accounting for 0.3% of the total mass of the reaction system, and reacting for 2h at 80°C under nitrogen protection to obtain a polydimethylsiloxane modified polyurethane acrylate prepolymer, the structural formula of which is as follows:

[0091]

[0092] Among them, R is R 1 for R 2 for n is 30.

[0093] The preparation method of the tung oil-based photoactive monomer is as follows: tung oil anhydride and pentaerythritol triacrylate are added into a three-necked flask at a molar ratio of 1:3, 1% of N,N-dimethylethanolamine and 0.5% of 4-methoxyphenol are added to the total mass of the reaction system (the total mass of tung oil anhydride and pentaerythritol triacrylate), the temperature is raised to 100°C, and the reaction is carried out at a speed of 280 rpm for 4 hours, then the temperature is lowered to 60°C, an equal molar amount of glycidyl methacrylate is added to the tung oil anhydride, and 1% of N,N-dimethylethanolamine and 0.5% of 4-methoxyphenol are added to the mass of glycidyl methacrylate, the temperature is raised to 100°C, and the reaction is carried out at a speed of 280 rpm for 4 hours to obtain a tung oil-based photoactive monomer, the structural formula of which is as follows:

[0094]

[0095] Among them, R 3 for R 4 for

[0096] Example 3

[0097] (1) Cleaning the surface of a glass slide, dipping the glass slide in an ethanol solution of γ-mercaptopropyltriethoxysilane with a mass concentration of 3%, dipping for 10 minutes, and then drying at 110° C. for 10 minutes to obtain a pretreated glass slide;

[0098] (2) adding 0.3 g of tung oil-based photoactive monomer, 0.2 g of photoinitiator TPO-L and 2 g of butyl acetate to a solution containing 0.7 g of polydimethylsiloxane-modified polyurethane acrylate prepolymer, stirring evenly to obtain a mixed coating;

[0099] (3) The mixed coating was sprayed on the pretreated glass slide at a pressure of 0.25 MPa, with a spraying amount of 0.002 g / cm 2 ;

[0100] (4) The coated glass slide was placed under a UV-LED lamp for 2 min to obtain a transparent coating.

[0101] The preparation method of the polydimethylsiloxane modified polyurethane acrylate prepolymer is as follows: dissolving aminopropyl diblocked polydimethylsiloxane in an appropriate amount of butyl acetate to obtain a siloxane solution (solid content is 8%), adding a butyl acetate solution of isophorone diisocyanate (the solid content of the butyl acetate solution of isophorone diisocyanate is 10%, and the molar ratio of aminopropyl diblocked polydimethylsiloxane to isophorone diisocyanate is 1:2) dropwise (dropping rate is 2s / drop) to the siloxane solution, and after the dropwise addition is completed, the reaction is carried out at room temperature at a rate of 300rpm with magnetic stirring for 2h, and then the reaction solution is transferred to a three-necked flask, and pentaerythritol triacrylate in an amount equal to the molar amount of isophorone diisocyanate and dibutyltin diacetate accounting for 0.3% of the total mass of the reaction system are added, and the reaction is carried out at 80°C for 2h under nitrogen protection to obtain a polydimethylsiloxane modified polyurethane acrylate prepolymer, the structural formula of which is as follows:

[0102]

[0103] Among them, R is R 1 for R 2 for n is 30.

[0104] The preparation method of the tung oil-based photoactive monomer is as follows: tung oil anhydride and pentaerythritol triacrylate are added into a three-necked flask at a molar ratio of 1:3, 1% of N,N-dimethylethanolamine and 0.5% of 4-methoxyphenol are added to the total mass of the reaction system (the total mass of tung oil anhydride and pentaerythritol triacrylate), the temperature is raised to 100°C, and the reaction is carried out at a speed of 280 rpm for 4 hours, then the temperature is lowered to 60°C, an equal molar amount of glycidyl methacrylate is added to the tung oil anhydride, and 1% of N,N-dimethylethanolamine and 0.5% of 4-methoxyphenol are added to the mass of glycidyl methacrylate, the temperature is raised to 100°C, and the reaction is carried out at a speed of 280 rpm for 4 hours to obtain a tung oil-based photoactive monomer, the structural formula of which is as follows:

[0105]

[0106] Among them, R 3 for R 4 for

[0107] Example 4

[0108] (1) Cleaning the surface of a glass slide, dipping the glass slide in an ethanol solution of γ-aminopropyltriethoxysilane with a mass concentration of 2%, dipping for 5 minutes, and then drying at 110° C. for 10 minutes to obtain a pretreated glass slide;

[0109] (2) adding 0.4 g of tung oil-based photoactive monomer, 0.2 g of photoinitiator TPO-L and 2 g of butyl acetate to a solution containing 0.6 g of polydimethylsiloxane-modified polyurethane acrylate prepolymer, stirring evenly to obtain a mixed coating;

[0110] (3) The mixed coating was sprayed on the pretreated glass slide at a pressure of 0.2 MPa, with a spraying amount of 0.002 g / cm 2 ;

[0111] (4) The coated glass slide was placed under a UV-LED lamp for 2 min to obtain a transparent coating.

[0112] The preparation method of the polydimethylsiloxane modified polyurethane acrylate prepolymer is as follows: dissolving aminopropyl diblocked polydimethylsiloxane in an appropriate amount of butyl acetate to obtain a siloxane solution (solid content is 8%), adding a butyl acetate solution of isophorone diisocyanate (the solid content of the butyl acetate solution of isophorone diisocyanate is 10%, and the molar ratio of aminopropyl diblocked polydimethylsiloxane to isophorone diisocyanate is 1:2) dropwise (dropping rate is 2s / drop) to the siloxane solution, and after the dropwise addition is completed, the reaction is carried out at room temperature at a rate of 300rpm with magnetic stirring for 2h, and then the reaction solution is transferred to a three-necked flask, and pentaerythritol triacrylate in an amount equal to the molar amount of isophorone diisocyanate and dibutyltin diacetate accounting for 0.3% of the total mass of the reaction system are added, and the reaction is carried out at 80°C for 2h under nitrogen protection to obtain a polydimethylsiloxane modified polyurethane acrylate prepolymer, the structural formula of which is as follows:

[0113]

[0114] Among them, R is R 1 for R 2 for n is 30.

[0115] The preparation method of the tung oil-based photoactive monomer is as follows: tung oil anhydride and β-hydroxypropyl methacrylate are added to a three-necked flask at a molar ratio of 1:3, 1% of N,N-dimethylethanolamine and 0.5% of 4-methoxyphenol are added to the total mass of the reaction system (the total mass of tung oil anhydride and β-hydroxypropyl methacrylate), the temperature is raised to 100°C, and the reaction is carried out at a speed of 280 rpm for 4 hours, and then the temperature is lowered to 60°C, and an equal molar amount of glycidyl methacrylate is added to the tung oil anhydride, and 1% of N,N-dimethylethanolamine and 0.5% of 4-methoxyphenol are added to the mass of glycidyl methacrylate, the temperature is raised to 100°C, and the reaction is carried out at a speed of 280 rpm for 4 hours to obtain a tung oil-based photoactive monomer, and the structural formula is as follows:

[0116]

[0117] Among them, R 3 for R 4 for

[0118] Example 5

[0119] (1) Cleaning the surface of a glass slide, dipping the glass slide in an ethanol solution of γ-methacryloxypropyltrimethoxysilane with a mass concentration of 2%, dipping for 10 minutes, and then drying at 110° C. for 10 minutes to obtain a pretreated glass slide;

[0120] (2) adding 0.5 g of tung oil-based photoactive monomer, 0.2 g of photoinitiator 819 and 2 g of butyl acetate to a solution containing 0.5 g of polydimethylsiloxane-modified polyurethane acrylate prepolymer, stirring evenly to obtain a mixed coating;

[0121] (3) The mixed coating was sprayed on the pretreated glass slide at a pressure of 0.25 MPa, with a spraying amount of 0.002 g / cm 2 ;

[0122] (4) The coated glass slide was placed under a UV-LED lamp for 2 min to obtain a transparent coating.

[0123] The preparation method of the polydimethylsiloxane modified polyurethane acrylate prepolymer is as follows: dissolving aminopropyl diblocked polydimethylsiloxane in an appropriate amount of butyl acetate to obtain a siloxane solution (solid content is 8%), adding a butyl acetate solution of hexamethylene diisocyanate (the solid content of the butyl acetate solution of hexamethylene diisocyanate is 10%, and the molar ratio of aminopropyl diblocked polydimethylsiloxane to hexamethylene diisocyanate is 1:2) dropwise (dropping rate is 2s / drop) to the siloxane solution A, and after the dropwise addition is completed, the reaction is carried out at room temperature at a rate of 300rpm with magnetic stirring for 2h, and then the reaction solution is transferred to a three-necked flask, and β-hydroxypropyl methacrylate in an amount equal to the molar amount of hexamethylene diisocyanate and dibutyltin diacetate accounting for 0.3% of the total mass of the reaction system are added, and the reaction is carried out at 80°C for 2h under nitrogen protection to obtain a polydimethylsiloxane modified polyurethane acrylate prepolymer, the structural formula of which is as follows:

[0124]

[0125] Among them, R is R 1 for R 2 for n is 30.

[0126] The preparation method of the tung oil-based photoactive monomer is as follows: tung oil anhydride and β-hydroxypropyl methacrylate are added to a three-necked flask at a molar ratio of 1:3, 1% of N,N-dimethylethanolamine and 0.5% of 4-methoxyphenol are added to the total mass of the reaction system (the total mass of tung oil anhydride and β-hydroxypropyl methacrylate), the temperature is raised to 100°C, and the reaction is carried out at a speed of 280 rpm for 4 hours, and then the temperature is lowered to 60°C, and an equal molar amount of glycidyl methacrylate is added to the tung oil anhydride, and 1% of N,N-dimethylethanolamine and 0.5% of 4-methoxyphenol are added to the mass of glycidyl methacrylate, the temperature is raised to 100°C, and the reaction is carried out at a speed of 280 rpm for 4 hours to obtain a tung oil-based photoactive monomer, and the structural formula is as follows:

[0127]

[0128] Among them, R 3 for R 4 for

[0129] Comparative Example 1

[0130] (1) Cleaning the surface of a glass slide, dipping the glass slide in an ethanol solution of γ-mercaptopropyltrimethoxysilane with a mass concentration of 2%, dipping for 10 minutes, and then drying at 110° C. for 10 minutes to obtain a pretreated glass slide;

[0131] (2) adding 0.2 g of photoinitiator TPO-L to a solution containing 1 g of polydimethylsiloxane-modified polyurethane acrylate prepolymer, stirring evenly, and obtaining a mixed coating;

[0132] (3) The mixed coating was sprayed on the pretreated glass slide at a pressure of 0.3 MPa, with a spraying amount of 0.002 g / cm 2 ;

[0133] (4) The coated glass slide was placed under a UV-LED lamp for 2 min to obtain a transparent coating.

[0134] The preparation method of the polydimethylsiloxane-modified polyurethane acrylate prepolymer and the structural formula of the obtained polydimethylsiloxane-modified polyurethane acrylate prepolymer are the same as those in Example 1.

[0135] Comparative Example 2

[0136] (1) Cleaning the surface of a glass slide, dipping the glass slide in an ethanol solution of γ-mercaptopropyltrimethoxysilane with a mass concentration of 2%, dipping for 10 minutes, and then drying at 110° C. for 10 minutes to obtain a pretreated glass slide;

[0137] (2) adding 0.2 g of photoinitiator TPO-L and 4 g of ethyl acetate to 1 g of tung oil-based photoactive monomer, stirring evenly to obtain a mixed coating;

[0138] (3) The mixed coating was sprayed on the pretreated glass slide at a pressure of 0.3 MPa, with a spraying amount of 0.002 g / cm 2 ;

[0139] (4) The coated glass slide was placed under a UV-LED lamp for 2 min to obtain a transparent coating.

[0140] The preparation method of the tung oil-based photoactive monomer and the structural formula of the obtained tung oil-based photoactive monomer are the same as those in Example 1.

[0141] The contact angle, anti-fingerprint performance and light transmittance of the coatings prepared in Examples 1 to 5 and Comparative Examples 1 to 2 were tested.

[0142] Contact angle test: The contact angles of the coatings prepared in Examples 1 to 5 and Comparative Examples 1 to 2 were measured using a contact angle measuring instrument JC2000D2. The results are shown in Table 1.

[0143] Table 1 Contact angles of coatings prepared in Examples 1 to 5 and Comparative Examples 1 to 2

[0144]

[0145]

[0146] It can be seen from Table 1 that the water contact angle of the coating formed by curing the polydimethylsiloxane-modified polyurethane acrylate prepolymer can reach about 110°, and the water contact angle of the coating formed by curing the tung oil-based photoactive monomer is about 100°. When the molar ratio of the polydimethylsiloxane-modified polyurethane acrylate prepolymer to the tung oil-based photoactive monomer is less than or equal to 5:5, the water contact angle of the coating is 108-110°.

[0147] Anti-fingerprint performance test: Hydroxyl-terminated polydimethylsiloxane, propylene glycol methyl ether and artificial sweat were mixed in a weight ratio of 3:3:4 to prepare artificial fingerprint liquid; artificial sweat was prepared by mixing 3mL / L lactic acid, 5mL / L acetic acid, 10g / L sodium chloride, 10g / L sodium hydrogen phosphate and deionized water. First, clean the finger with alcohol, immerse the finger in the artificial fingerprint liquid, and then touch the coating surface to form a fingerprint, and then wipe it with a paper towel at a speed of 3cm / s under a load of 200g, and record the number of wipes that can make the fingerprint disappear. The results are shown in Table 2.

[0148] Table 2 Anti-fingerprint properties of coatings prepared in Examples 1 to 5 and Comparative Examples 1 to 2

[0149]

[0150]

[0151] As shown in Table 2, after adding tung oil-based photoactive monomers, the crosslinking density of the coating is increased, and the coating is free from damage after wiping. The coating formed by curing only tung oil-based photoactive monomers needs to be wiped 6 times to remove fingerprints, while when the molar ratio of polydimethylsiloxane-modified polyurethane acrylate prepolymer to tung oil-based photoactive monomer is less than or equal to 6:4, the coating can be wiped clean only 3 times, and has excellent anti-fingerprint performance.

[0152] Light transmittance test: The light transmittance of the coatings of Examples 1 to 5 and Comparative Examples 1 to 2 was measured using an ultraviolet-visible spectrophotometer, with the transmittance at 550 nm being the standard. The results are shown in Table 3.

[0153] Table 3 Light transmittance of coatings prepared in Examples 1 to 5 and Comparative Examples 1 to 2

[0154] Light transmittance test Transmittance at 550nm / % Comparative Example 1 92.72 Comparative Example 2 91.40 Example 1 85.77 Example 2 86.14 Example 3 86.34 Example 4 86.89 Example 5 87.22

[0155] It can be seen from Table 3 that the light transmittance of the coatings prepared in Examples 1 to 5 and Comparative Examples 1 to 2 at 550 nm is all above 85%, and the coatings have excellent transparency.

[0156] The tung oil derivative composite fluorine-free anti-fingerprint transparent coating material provided by the present invention is compounded with polydimethylsiloxane modified polyurethane acrylate prepolymer, tung oil-based photoactive monomer, photoinitiator, and organic solvent, and is cured by ultraviolet light. The prepared polymer coating has low surface energy and environmental protection. Under ultraviolet light irradiation, it can be quickly photocured to reach a surface dry state, thereby improving production efficiency. The prepared coating is transparent and has excellent hydrophobic effect and anti-fingerprint performance. The results of the embodiment show that the transparent coating has a water contact angle of nearly 110°, a light transmittance of more than 85%, and an anti-fingerprint performance that can remove fingerprints by wiping with a paper towel less than 4 times.

[0157] 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 principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a tung oil derivative composite fluorine-free anti-fingerprint transparent coating material, characterized in that: The following steps are involved: 1) mixing a polydimethylsiloxane-modified polyurethane acrylate prepolymer, a tung oil-based photoactive monomer, a photoinitiator and an organic solvent to obtain a mixed coating; The substrate is surface treated by using a silane coupling agent solution to obtain a pretreated substrate; 2) applying the mixed coating to the pretreated substrate and performing UV curing to obtain a tung oil derivative composite fluorine-free anti-fingerprint transparent coating material; The mass of the tung oil-based photoactive monomer is 10 to 50% of the total mass of the polydimethylsiloxane-modified polyurethane acrylate prepolymer and the tung oil-based photoactive monomer; The preparation method of the tung oil-based photoactive monomer comprises the following steps: Conducting a first reaction of tung oil anhydride, hydroxy acrylate monomer, a first part of catalyst and a first part of polymerization inhibitor to obtain an intermediate; The intermediate, glycidyl methacrylate, a second part of the catalyst and a second part of the polymerization inhibitor are subjected to a second reaction to obtain a tung oil-based photoactive monomer.

2. The preparation method according to claim 1, characterized in that: The molar ratio of tung oil anhydride to hydroxy acrylate monomer is 1:2-4, and the molar ratio of tung oil anhydride to glycidyl methacrylate is 0.8-1.2:0.8-1.

2.

3. The preparation method according to claim 1 or 2, characterized in that: The mass of the first part of the catalyst is 0.8-1.2% of the total mass of tung oil anhydride and hydroxy acrylate monomers, and the mass of the first part of the inhibitor is 0.3-0.8% of the total mass of tung oil anhydride and hydroxy acrylate monomers; the mass of the second part of the catalyst is 0.8-1.2% of the mass of glycidyl methacrylate, and the mass of the second part of the inhibitor is 0.3-0.8% of the mass of glycidyl methacrylate.

4. The preparation method according to claim 3, characterized in that: The hydroxy acrylate monomer includes one or more of β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl methacrylate and pentaerythritol triacrylate; the catalyst is N,N-dimethylethanolamine; and the inhibitor includes hydroquinone and / or 4-methoxyphenol.

5. The preparation method according to claim 3, characterized in that: The temperature of the first reaction is 100-120° C., and the time of the first reaction is 3-5 hours; the temperature of the second reaction is 90-110° C., and the time of the second reaction is 3-4 hours.

6. The preparation method according to claim 1 or 5, characterized in that: The preparation method of the polydimethylsiloxane-modified polyurethane acrylate prepolymer comprises the following steps: Mixing aminopropyl di-terminated polydimethylsiloxane, butyl acetate and diisocyanate to carry out a first reaction to obtain an intermediate; The intermediate, hydroxy acrylate monomer and organotin catalyst are mixed, and a second reaction is carried out under nitrogen protection to obtain a polydimethylsiloxane-modified polyurethane acrylate prepolymer; The first reaction is carried out at room temperature for 1 to 3 hours; the second reaction is carried out at a temperature of 60 to 80° C. for 1 to 3 hours.

7. The preparation method according to claim 6, characterized in that: The diisocyanate includes one or more of isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hexamethylene diisocyanate and lysine diisocyanate; the hydroxy acrylate monomer includes one or more of β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentahexaenoate, trimethylolpropane triacrylate and ditrimethylolpropane tetraacrylate; the organic tin catalyst includes one or more of dibutyltin dilaurate, stannous octoate and dibutyltin diacetate.

8. The preparation method according to claim 1 or 7, characterized in that: The photoinitiator includes one or more 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-diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; the mass of the photoinitiator is 15-25% of the total mass of the polydimethylsiloxane-modified polyurethane acrylate prepolymer and the tung oil-based photoactive monomer; The organic solvent comprises one or more of acetone, 2-butanone, tetrahydrofuran, ethyl acetate, butyl acetate and isopropyl acetate; the mass of the organic solvent is 1 to 4 times the total mass of the polydimethylsiloxane-modified polyurethane acrylate prepolymer and the tung oil-based photoactive monomer.

9. The tung oil derivative composite fluorine-free anti-fingerprint transparent coating material prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the tung oil derivative composite fluorine-free anti-fingerprint transparent coating material according to claim 9 in anti-fingerprint materials.

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