A UV-curable organic / inorganic hybrid low-fluorine wear-resistant and fingerprint-resistant coating and its preparation method

Abstract

The application provides a UV-cured organic / inorganic hybrid low-fluorine-containing wear-resistant anti-fingerprint coating and a preparation method thereof, and belongs to the technical field of photocured resins and coatings. The UV-cured organic / inorganic hybrid low-fluorine-containing wear-resistant anti-fingerprint coating is compounded by a fluorine-containing polyurethane acrylate oligomer, an active diluent, modified silica sol, a photoinitiator, a leveling agent and a defoaming agent, and then the coating is obtained through UV curing. The hybrid UV coating obtained by the application has low inorganic components and low fluorine content, and shows high transparency, high hardness, high wear resistance and excellent anti-fingerprint performance. The water contact angle of the coating is greater than 110 degrees, the light transmittance is greater than 90%, and the hydrophobicity can still be maintained after 2000 times of steel wool rubbing; the fingerprint mark can be removed by wiping with a paper towel for less than 1 time.

Description

Technical Field

[0001] This invention relates to the field of UV-curable resins and coatings, and in particular to a UV-curable organic / inorganic hybrid low-fluorine wear-resistant and fingerprint-resistant coating and its preparation method. Background Technology

[0002] With technological advancements and social development, polymer-based coatings have garnered widespread attention and found applications in various fields due to their unique properties. One of the core functions of these coatings is to provide protection for the substrate. However, compared to metal and ceramic-based coatings, polymer-based coatings typically exhibit weaker mechanical properties such as hardness and abrasion resistance due to the inherent properties of polymer materials. Friction between material contact surfaces leads to surface wear, which not only shortens the material's lifespan but also results in significant energy consumption on a macroscopic level. Therefore, researching and developing polymer-based coatings with improved mechanical properties is of great importance for enhancing material durability and energy efficiency.

[0003] UV curing has been widely used in the preparation of transparent coatings, but the problem of transparent coatings being easily contaminated by fingerprints and other stains cannot be ignored. In recent years, some researchers have proposed some studies to address the fingerprint resistance of coatings. Chen Weidu used isocyanate-modified organosilicon resin compositions, which can significantly improve the surface hardness and scratch resistance of plastics; however, the coating cannot simultaneously possess low refractive index, high light transmittance, high surface hardness, strong scratch resistance, and hydrophobic, oleophobic, and antifouling properties, thus failing to meet the requirements for protective coatings. Patent US15029867 proposes a fluorinated anti-fingerprint additive for UV coatings, which can improve the fingerprint resistance and abrasion resistance of the coating. However, this compound is only used as a functional additive and is not the main resin component of UV coatings, so the abrasion resistance of the coating is not ideal and cannot meet the requirements for high abrasion resistance. Fluorinated compounds are widely used due to their low surface energy, high stability, and hydrophobicity. However, the use of large doses of fluorinated compounds can cause environmental pollution, bioaccumulation, health risks, and ecological damage, requiring effective measures to reduce their emissions and pollution. Therefore, how to obtain a UV-curable organic / inorganic hybrid low-fluorine wear-resistant and fingerprint-resistant coating and its preparation method are currently technical problems that need to be solved. Summary of the Invention

[0004] The purpose of this invention is to provide a UV-curable organic / inorganic hybrid low-fluorine wear-resistant and fingerprint-resistant coating and its preparation method, in order to solve the technical problems of high fluorine content and poor surface wear resistance of existing fingerprint coatings.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a UV-curable organic / inorganic hybrid low-fluorine wear-resistant and fingerprint-resistant coating, prepared from raw materials comprising the following mass percentages:

[0007]

[0008] Furthermore, the preparation method of the fluorinated polyurethane acrylate oligomer includes the following steps:

[0009] S1. Under N2 environment, perfluoropolyether diol, polycarbonate diol, diisocyanate and organometallic catalyst are mixed and reacted to obtain NCO-terminated prepolymer.

[0010] S2. Add polymerization inhibitor and end-capping agent monomers to the above prepolymer and react to obtain fluorinated polyurethane acrylate resin.

[0011] The molar ratio of the perfluoropolyether diol to the polycarbonate diol is 1:5 to 10; the molar ratio of the polycarbonate diol to the diisocyanate is 1:1 to 2; and the amount of the organometallic catalyst is 0.1 to 2% of the total mass of the perfluoropolyether diol, the polycarbonate diol, and the diisocyanate.

[0012] The amount of the polymerization inhibitor is 0.01 to 0.1% of the prepolymer mass, and the molar ratio of diisocyanate to end-capping agent monomer is 2:1 to 2.

[0013] Furthermore, the perfluoropolyether diol comprises one or more of the following: Italian SOLVAY FLUOROLINK D4000, domestic Yuyao Huihong FD-162, FD-163, FD-164, and domestic Wuhan Lana White No. 1937.

[0014] The polycarbonate diol comprises one or more of the following: Ube PCDL series UH-200, PH-200 and BH-200; Asahi Kasei G3452, G3450J, T4672, T4692, T4691 and T5652; Kuraray C-2050 and C-2090; and domestically produced Guangdong Wengjiang PC06349 and Munafei MNF3230.

[0015] The diisocyanate comprises one or more of isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and hexamethylene diisocyanate; the organometallic catalyst comprises one or more of dibutyltin dilaurate, stannous octoate, and organobismuth.

[0016] Furthermore, the polymerization inhibitor comprises one or more of 4-methoxyphenol, hydroquinone, and 2,6-di-tert-butyl-p-methylphenol; the end-capping agent monomer comprises one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, 2-ethoxyethyl acrylate, 2-cyanoacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.

[0017] Furthermore, in step S1, the reaction temperature is 70–90°C and the reaction time is 2–4 hours; in step S2, the reaction temperature is 60–80°C and the reaction time is 3–5 hours.

[0018] Furthermore, the preparation method of the modified silica sol includes the following steps:

[0019] S3. Tetraethyl orthosilicate and anhydrous ethanol are mixed at 20-40°C while stirring and heating. After reaching the reaction temperature, hydrochloric acid solution catalyst is added dropwise to adjust the pH to 3-4. After the addition is completed, the reaction is continued for a certain period of time to obtain the hydrolysis solution.

[0020] S4. Add silanes with different functional groups dropwise to the hydrolysis solution to carry out the reaction, and then age to obtain modified silica sol;

[0021] In step S3, the mixing time is 15-30 min, the reaction temperature is 30-50℃, and the reaction continues for 2-3 h; in step S4, the reaction temperature is 50-70℃, the reaction time is 4-8 h, and the aging time is 3-5 days.

[0022] Furthermore, the molar ratio of the tetraethyl orthosilicate, the silane with different functional groups, and anhydrous ethanol is 1:0.1 to 5:1 to 10; the silane comprises one or more of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, methacryloyloxypropyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, perfluorodecyltriethoxysilane, (3-mercaptopropyl)trimethoxysilane, tridecafluorooctyltrimethoxysilane, perfluoropolyethertrimethoxysilane, dodecyltrimethoxysilane, and dodecyltriethoxysilane.

[0023] Furthermore, the reactive diluent comprises one or more of isobornyl acrylate, dicyclopentenyl acrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, and trimethylolpropane triacrylate.

[0024] The photoinitiator comprises one or more of 1-hydroxycyclohexylphenyl ketone, benzoin diethyl ether, 2-hydroxy-2-methyl-1-phenylpropanone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylphenylpropanone, 2,4,6-trimethylbenzoyl-diphenylphosphine, and ethyl 2,4,6-trimethylbenzoylphenylphosphonate; the leveling agent comprises one or more of BYK-3455, BYK-3550, and BYK333 (Germany); and the defoamer comprises one or more of Dow AFE-1430 (USA), BYK-066N (Germany), Datian AT-99 (China), and AS-6800 (Germany).

[0025] This invention also provides a method for preparing a UV-cured organic / inorganic hybrid low-fluorine wear-resistant and fingerprint-resistant coating, comprising the following steps:

[0026] Fluorinated polyurethane acrylate oligomer, reactive diluent, modified silica sol, photoinitiator, leveling agent and defoamer are mixed, allowed to stand in the dark and stirred until homogeneous and transparent to obtain the sample;

[0027] After the sample is coated onto the surface of a dry substrate and cured under ultraviolet light, a UV-cured organic / inorganic hybrid low-fluorine wear-resistant and fingerprint-resistant coating is obtained.

[0028] Furthermore, the UV curing time is 30–300 seconds.

[0029] The beneficial effects of this invention are:

[0030] The UV-curable organic / inorganic hybrid low-fluorine wear-resistant hydrophobic coating material provided by this invention is a compound of fluorinated polyurethane acrylate oligomers, reactive diluents, modified silica sol, photoinitiators, leveling agents, and defoamers, cured under ultraviolet light. The coating prepared from fluorinated polyurethane acrylate oligomers and reactive diluents has transparency and low surface energy. Furthermore, the introduction of modified silica sol increases the inorganic components of the coating without affecting its light transmittance. Simultaneously, it reduces the volume shrinkage rate of the coating and improves its hardness and wear resistance. The results of the embodiments show that it possesses a contact angle exceeding 110°, a light transmittance of over 90%, and maintains hydrophobicity even after 2000 cycles of rubbing with 0000# steel wool at a weight of 1 kg; it also exhibits excellent anti-fingerprint performance, removing fingerprints with less than one wipe using a paper towel.

[0031] This invention introduces perfluorinated polyether diol into polycarbonate diol using a chemical method, and the resulting fluorinated polyurethane acrylate oligomer has both low surface energy and chemical resistance.

[0032] This invention improves the compatibility of organic and inorganic components with vastly different properties by using sol-gel technology to prepare modified silica sol. This reaction can occur at room temperature. The resulting hybrid coating combines the high hardness, wear resistance, scratch resistance, high-temperature resistance, and solvent resistance of inorganic materials with the good flexibility and processability of organic materials. The preparation method is simple, and combined with UV curing technology, it greatly saves solvent and energy usage, making the preparation process more environmentally friendly. Detailed Implementation

[0033] This invention provides a UV-curable organic / inorganic hybrid low-fluorine wear-resistant and fingerprint-resistant coating, prepared from raw materials comprising the following mass percentages:

[0034]

[0035] In this invention, the amount of the fluorinated polyurethane acrylate oligomer is preferably 35-80% by mass percentage, more preferably 40-75%, and even more preferably 45-70%.

[0036] In this invention, the amount of the active diluent is preferably 15-25% by mass percentage, more preferably 18-22%, and even more preferably 20%.

[0037] In this invention, the amount of the modified silica sol is preferably 5-25% by mass percentage, more preferably 10-20%, and even more preferably 15%.

[0038] In this invention, the amount of photoinitiator is preferably 2-3% by mass percentage, more preferably 2.5-2.8%.

[0039] In this invention, the amount of leveling agent used is preferably 0.2-0.4% by mass percentage, and more preferably 0.3%.

[0040] In this invention, the amount of the defoamer is preferably 0.2-0.4% by mass percentage, and more preferably 0.3%.

[0041] The preparation method of the fluorinated polyurethane acrylate oligomer includes the following steps:

[0042] S1. Under N2 environment, perfluoropolyether diol, polycarbonate diol, diisocyanate and organometallic catalyst are mixed and reacted to obtain NCO-terminated prepolymer.

[0043] S2. Add polymerization inhibitors and end-capping agents to the above prepolymer and react to obtain fluorinated polyurethane acrylate resin.

[0044] In this invention, the molar ratio of the perfluoropolyether diol and the polycarbonate diol is 1:5 to 10, preferably 1:6 to 9, and more preferably 1:7 to 8; the molar ratio of the polycarbonate diol and the diisocyanate is 1:1 to 2, preferably 1:1.2 to 1.8, and more preferably 1:1.5; the amount of the organometallic catalyst is 0.1 to 2% of the total mass of the perfluoropolyether diol, the polycarbonate diol, and the diisocyanate, preferably 0.2 to 1%, and more preferably 0.2 to 0.3%.

[0045] In this invention, the amount of the polymerization inhibitor is 0.01 to 0.1% of the prepolymer mass, preferably 0.02 to 0.08%, more preferably 0.03 to 0.06%, and the molar ratio of diisocyanate to end-capping agent monomer is 2:1 to 2, preferably 2:1.

[0046] In this invention, the perfluoropolyether diol is preferably one or more of the following: Italian SOLVAYFLUOROLINKD 4000, domestic Yuyao Huihong FD-162, FD-163, FD-164, and domestic Wuhan Lana White No. 1937.

[0047] The polycarbonate diol is preferably one or more of the following: UH-200, PH-200 and BH-200 from the Ube PCDL series; G3452, G3450J, T4672, T4692, T4691 and T5652 from Asahi Kasei; C-2050 and C-2090 from Kuraray; and domestically produced Guangdong Wengjiang PC06349 and MNF3230.

[0048] The diisocyanate is preferably one or more of isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and hexamethylene diisocyanate; the organometallic catalyst comprises one or more of dibutyltin dilaurate, stannous octoate, and organobismuth.

[0049] In this invention, the polymerization inhibitor is preferably one or more of 4-methoxyphenol, hydroquinone, and 2,6-di-tert-butyl-p-methylphenol; the end-capping agent monomer comprises one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, 2-ethoxyethyl acrylate, 2-cyanoacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate. In this invention, when the raw materials are two or more of the above, there is no special limitation on the different raw material ratios; adjustments can be made according to actual needs.

[0050] In this invention, in step S1, the reaction temperature is 70-90°C, preferably 75-85°C, and more preferably 80°C; the reaction time is 2-4 hours, preferably 3 hours; in step S2, the reaction temperature is 60-80°C, preferably 65-75°C, and more preferably 70-72°C; the reaction time is 3-5 hours, preferably 4 hours.

[0051] In this invention, in step S1, the reaction is carried out under stirring, and the stirring speed is 200-400 rpm, preferably 300 rpm.

[0052] In this invention, the preparation method of the modified silica sol includes the following steps:

[0053] S3. Tetraethyl orthosilicate and anhydrous ethanol are mixed at 20-40°C while stirring and heating. After reaching the reaction temperature, hydrochloric acid solution catalyst is added dropwise to adjust the pH to 3-4. After the addition is completed, the reaction is continued for a certain period of time to obtain the hydrolysis solution.

[0054] S4. Silanes with different functional groups are added dropwise to the hydrolysis solution to carry out the reaction, and the modified silica sol is obtained by aging.

[0055] In this invention, in step S3, the mixing time is 15-30 min, preferably 20-25 min; the reaction temperature is 30-50℃, preferably 35-45℃; the reaction time continues for 2-3 h, preferably 2 h; in step S4, the reaction temperature is 50-70℃, preferably 55-65℃, more preferably 60-62℃; the reaction time is 4-8 h, preferably 5-7 h, more preferably 6 h; the aging time is 3-5 days, preferably 4 days.

[0056] In this invention, the molar ratio of tetraethyl orthosilicate, silanes with different functional groups and anhydrous ethanol is 1:0.1-5:1-10, preferably 1:0.25-4:2-9, and more preferably 1:0.25-3:4-8.

[0057] In this invention, the silane is preferably one or more of the following: methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, methacryloxypropyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, perfluorodecyltriethoxysilane, (3-mercaptopropyl)trimethoxysilane, tridecafluorooctyltrimethoxysilane, perfluoropolyethertrimethoxysilane, dodecyltrimethoxysilane, and dodecyltriethoxysilane. In this invention, when two or more of the above-mentioned raw materials are used, there is no special limitation on the different raw material ratios; adjustments can be made according to actual needs.

[0058] In this invention, the reactive diluent is preferably one or more of isobornyl acrylate, dicyclopentenyl acrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, and trimethylolpropane triacrylate.

[0059] The photoinitiator is preferably one or more of 1-hydroxycyclohexylphenyl ketone, benzoin diethyl ether, 2-hydroxy-2-methyl-1-phenylpropanone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylphenylpropanone, 2,4,6-trimethylbenzoyl-diphenylphosphine, and ethyl 2,4,6-trimethylbenzoylphenylphosphonate; the leveling agent comprises one or more of BYK-3455, BYK-3550, and BYK333 (Germany); the defoamer comprises one or more of Dow AFE-1430 (USA), BYK-066N (Germany), Datian AT-99 (China), and AS-6800 (Germany). In this invention, when two or more of the above-mentioned raw materials are used, there are no special limitations on the different raw material ratios; adjustments can be made according to actual needs.

[0060] This invention also provides a method for preparing a UV-cured organic / inorganic hybrid low-fluorine wear-resistant and fingerprint-resistant coating, comprising the following steps:

[0061] Fluorinated polyurethane acrylate oligomer, reactive diluent, modified silica sol, photoinitiator, leveling agent and defoamer are mixed, allowed to stand in the dark and stirred until homogeneous and transparent to obtain the sample;

[0062] After the sample is coated onto the surface of a dry substrate and cured under ultraviolet light, a UV-cured organic / inorganic hybrid low-fluorine wear-resistant and fingerprint-resistant coating is obtained.

[0063] In this invention, the ultraviolet curing is preferably carried out under a UV-LED lamp, and the curing time is 30–300 s, preferably 50–200 s, and more preferably 150–180 s. During the ultraviolet curing process, the photoinitiator absorbs ultraviolet light and transforms into free radicals, which initiate cross-linking of the double bonds in the fluorinated polyurethane acrylate oligomer, reactive diluent, and modified silica sol, thereby curing the coating.

[0064] In this invention, the coating is performed by applying the sample to the surface of a substrate that has been repeatedly cleaned and dried using a 30μm wet film preparation device. The substrate may be a plastic substrate, a glass substrate, or a metal substrate.

[0065] In this invention, the coating method is preferably smearing; the thickness of the smear is preferably 25-100 μm, more preferably 25-50 μm, and even more preferably 30 μm.

[0066] In this invention, the substrate is preferably glass, metal, or plastic.

[0067] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0068] Example 1

[0069] (1) Clean the surface of the glass slide thoroughly and dry it for later use;

[0070] (2) Add 0.5g (15.60%) of 1,6-hexanediol diacrylate and 0.125g (3.90%) of modified silica sol to 2.5g (78.00%) of fluorinated polyurethane acrylate oligomer and let stand in a container for 30min. Add 0.06g (1.88%) of photoinitiator 1-hydroxycyclohexylphenyl ketone, 0.01g (0.31%) of leveling agent BYK333 and 0.01g (0.31%) of defoamer AFE-1430 to the container and stir magnetically in the dark until homogeneous and transparent to obtain a mixed coating.

[0071] (3) Apply the mixed coating to the cleaned glass slide with a thickness of 30±1um;

[0072] (4) Place the coated substrate under a UV-LED lamp for 90 seconds to obtain a transparent coating.

[0073] The preparation process of fluorinated polyurethane acrylate oligomers includes the following steps:

[0074] Under N2 atmosphere, 0.3 g (0.5 mmol) of perfluoropolyether diol FD-162 (Mn = 600 g / mol), 9 g (4.5 mmol) of dehydrated polycarbonate diol UH-200 (Mn = 2000 g / mol), and 2.24 g (10 mmol) of isophorone diisocyanate were sequentially added to a three-necked flask, followed by the addition of 0.3% dibutyltin dilaurate. The mixture was mechanically stirred at 300 rpm and reacted at 80 °C for 3 h. When the NCO% titration reached the theoretical value, 1.3 g (10 mmol) of the end-capping agent hydroxyethyl methacrylate and 0.1% hydroquinone were added, and the reaction was continued at 70 °C for 4 h. The reaction was terminated when the NCO% titration was ≤0.06%, yielding a fluorinated polyurethane acrylate oligomer with the following structure:

[0075]

[0076] The structures of R1 and R2 are as follows:

[0077]

[0078] Where x, y, p, and q represent integers representing the number of times a unit is repeated. The R1 and R2 structures throughout the paper are of this type, and will not be elaborated further.

[0079] The structure of R is

[0080]

[0081] The modified silica sol preparation process includes the following steps:

[0082] 10.4 g (0.05 mol) of tetraethyl orthosilicate and 6.9 g (0.15 mol) of anhydrous ethanol were added to a three-necked flask, heated to 40 °C, and stirred for 15 min at 500 rpm. Then, an acid solution consisting of 0.062 ml of hydrochloric acid and 3.15 g (0.175 mol) of deionized water was added dropwise, and the mixture was stirred for 2 h. Subsequently, 12.42 g (0.05 mol) of 3-(methacryloyloxy)propyltrimethoxysilane was added, and the mixture was heated to 60 °C and reacted for 6 h. The mixture was then discharged and aged for 4 days to obtain a modified silica sol, the structure of which is as follows:

[0083]

[0084] Among them M and M 1 The structure is as follows:

[0085]

[0086] Example 2

[0087] (1) Clean the surface of the glass slide thoroughly and dry it for later use;

[0088] (2) Add 1.0g (13.81%) trimethylolpropane triacrylate and 1.0g (13.81%) modified silica sol to 5.0g (69.06%) fluorinated polyurethane acrylate oligomer and let stand in a container for 30min. Add 0.21g (2.9%) photoinitiator benzoin diethyl ether, 0.02g (0.28%) leveling agent BYK-3550 and 0.01g (0.14%) defoamer BYK-066N to the container and stir magnetically in the dark until homogeneous and transparent to obtain a mixed coating.

[0089] (3) Apply the mixed coating to the cleaned glass slide with a thickness of 30±1um;

[0090] (4) Place the coated substrate under a UV-LED lamp for 90 seconds to obtain a transparent coating.

[0091] The preparation process of fluorinated polyurethane acrylate oligomers includes the following steps:

[0092] Under a nitrogen atmosphere, 1.0 g (0.5 mmol) of perfluoropolyether diol FD-164 (Mn = 2000 g / mol), 9 g (4.5 mmol) of dehydrated polycarbonate diol PH-200 (Mn = 2000 g / mol), and 2.24 g (10 mmol) of isophorone diisocyanate were sequentially added to a three-necked flask. 0.3% dibutyltin dilaurate was added, and the mixture was mechanically stirred at 300 rpm. The reaction was carried out at 80 °C for 3 h. The NCO% titration reached the theoretical value. Then, 2.98 g (10 mmol) of pentaerythritol triacrylate (the end-capping agent) and 0.05% 4-methoxyphenol were added dropwise. The reaction was carried out at 70 °C for 4 h. The reaction was terminated when the NCO% titration was ≤0.06%, yielding a fluorinated polyurethane acrylate oligomer with the following structure:

[0093]

[0094] Where R 1 The structure is as follows:

[0095]

[0096] The modified silica sol preparation process includes the following steps:

[0097] 10.4 g (0.05 mol) of tetraethyl orthosilicate and 6.9 g (0.15 mol) of anhydrous ethanol were added to a three-necked flask, heated to 40 °C, and stirred for 15 min at 500 rpm. Then, an acid solution consisting of 0.062 ml of hydrochloric acid and 3.15 g (0.175 mol) of deionized water was added dropwise, and the mixture was stirred for 2 h. Subsequently, 7.41 g (0.05 mol) of vinyltrimethoxysilane was added, and the mixture was heated to 60 °C and reacted for 6 h. The mixture was then discharged and aged for 4 days to obtain a modified silica sol, the structure of which is as follows:

[0098]

[0099] Among them M and M 2 The structure is as follows:

[0100]

[0101] Example 3

[0102] (1) Clean the surface of the glass slide thoroughly and dry it for later use;

[0103] (2) Add 1.0g (14.86%) of acrylate isoborneol ester and 0.5g (7.43%) of modified silica sol to 5.0g (74.29%) of fluorinated polyurethane acrylate oligomer and let stand in a container for 30min. Add 0.20g (2.97%) of photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone, 0.01g (0.15%) of leveling agent BYK-3455 and 0.02g (0.3%) of defoamer AT-99 to the container and stir magnetically in the dark until homogeneous and transparent to obtain a mixed coating.

[0104] (3) Apply the mixed coating to the cleaned glass slide with a thickness of 30±1um;

[0105] (4) Place the coated substrate under a UV-LED lamp for 90 seconds to obtain a transparent coating.

[0106] The preparation process of fluorinated polyurethane acrylate oligomers includes the following steps:

[0107] Under a nitrogen atmosphere, 0.65 g (0.5 mmol) of perfluoropolyether diol FD-163 (Mn = 1300 g / mol), 9 g (4.5 mmol) of dehydrated polycarbonate diol BH-200 (Mn = 2000 g / mol), and 2.24 g (10 mmol) of isophorone diisocyanate were sequentially added to a three-necked flask. 0.3% dibutyltin dilaurate was added, and the mixture was mechanically stirred at 300 rpm. The reaction was carried out at 80 °C for 3 h. The NCO% titration reached the theoretical value. Then, 5.24 g (10 mmol) of dipentaerythritol pentaacrylate was added dropwise as a capping agent, along with 0.1% 2,6-di-tert-butyl-p-methylphenol. The reaction was carried out at 70 °C for 4 h. The reaction ended when the NCO% titration was ≤0.06%, yielding a fluorinated polyurethane acrylate oligomer with the following structure:

[0108]

[0109] Where R 2 The structure is as follows:

[0110]

[0111] The modified silica sol preparation process includes the following steps:

[0112] 10.4 g (0.05 mol) of tetraethyl orthosilicate and 6.9 g (0.15 mol) of anhydrous ethanol were added to a three-necked flask, heated to 40 °C, and stirred for 15 min at 500 rpm. Then, an acid solution consisting of 0.062 ml of hydrochloric acid and 3.15 g (0.175 mol) of deionized water was added dropwise, and the mixture was stirred for 2 h. Subsequently, 17.33 g (0.05 mol) of hexadecyltrimethoxysilane was added, and the mixture was heated to 60 °C and reacted for 6 h. The mixture was then discharged and aged for 4 days to obtain a modified silica sol, the structure of which is as follows:

[0113]

[0114] Among them M and M 3 The structure is as follows:

[0115]

[0116] Example 4

[0117] (1) Clean the surface of the glass slide thoroughly and dry it for later use;

[0118] (2) Add 0.5g (14.30%) diethylene glycol diacrylate and 0.375g (10.73%) modified silica sol to 2.5g (71.53%) fluorinated polyurethane acrylate oligomer and let stand in a container for 30min. Add 0.1g (2.86%) photoinitiator 2-hydroxy-4-(2-hydroxyethoxy)-2-methylphenylacetone, 0.01g (0.29%) leveling agent BYK333 and 0.01g (0.29%) defoamer AS-6800 to the container and stir magnetically in the dark until homogeneous and transparent to obtain a mixed coating.

[0119] (3) Apply the mixed coating to the cleaned glass slide with a thickness of 30±1um;

[0120] (4) Place the coated substrate under a UV-LED lamp for 90 seconds to obtain a transparent coating.

[0121] The preparation process of fluorinated polyurethane acrylate oligomers includes the following steps:

[0122] Under a nitrogen atmosphere, 0.52 g (0.5 mmol) of perfluorinated polyether diol Wuhan Lana White 1937 (Mn = 1040 g / mol), 9 g (4.5 mmol) of dehydrated polycarbonate diol G3452 (Mn = 2000 g / mol), and 2.24 g (10 mmol) of isophorone diisocyanate were sequentially added to a three-necked flask. 0.3% dibutyltin dilaurate was added, and the mixture was mechanically stirred at 300 rpm. The reaction was carried out at 80 °C for 3 h. The NCO% titration reached the theoretical value. Then, 0.65 g (5 mmol) of hydroxyethyl methacrylate and 1.49 g (5 mmol) of pentaerythritol triacrylate were added dropwise as end-capping agents, along with 0.05% hydroquinone. The reaction was carried out at 70 °C for 4 h. The reaction ended when the NCO% titration was ≤0.06%, yielding a fluorinated polyurethane acrylate oligomer with the following structure:

[0123]

[0124] Where R a and R b The structure is as follows:

[0125]

[0126] The modified silica sol preparation process includes the following steps:

[0127] 10.4 g (0.05 mol) of tetraethyl orthosilicate and 6.9 g (0.15 mol) of anhydrous ethanol were added to a three-necked flask, heated to 40 °C, and stirred for 15 min at 500 rpm. Then, an acid solution consisting of 0.062 ml of hydrochloric acid and 3.15 g (0.175 mol) of deionized water was added dropwise, and the mixture was stirred for 2 h. Subsequently, 9.36 g (0.02 mol) of tridecafluorooctyltrimethoxysilane was added dropwise, and the mixture was heated to 60 °C and reacted for 6 h. The mixture was then discharged and aged for 4 days to obtain a modified silica sol, the structure of which is as follows:

[0128]

[0129] Among them M and M 4 The structure is as follows:

[0130]

[0131] Example 5

[0132] (1) Clean the surface of the glass slide thoroughly and dry it for later use;

[0133] (2) Add 1.0g (14.54%) dicyclopentenyl acrylate and 0.75g (10.90%) modified silica sol to 5.0g (72.67%) fluorinated polyurethane acrylate oligomer and let stand for 30min. Add 0.1g (1.45%) photoinitiator ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 0.01g (0.14%) leveling agent BYK-3455 and 0.02g (0.3%) defoamer AFE-1430 to the container and stir magnetically in the dark until homogeneous and transparent to obtain a mixed coating.

[0134] (3) Apply the mixed coating to the cleaned glass slide with a thickness of 30±1 μm.

[0135] (4) Place the coated substrate under a UV-LED lamp for 90 seconds to obtain a transparent coating.

[0136] The preparation process of fluorinated polyurethane acrylate oligomers includes the following steps:

[0137] Under a nitrogen atmosphere, 0.65 g (0.5 mmol) of perfluoropolyether diol FD-163 (Mn = 1300 g / mol), 9 g (4.5 mmol) of dehydrated polycarbonate diol PC06349 (Mn = 2000 g / mol), and 2.24 g (10 mmol) of isophorone diisocyanate were sequentially added to a three-necked flask. 0.3% dibutyltin dilaurate was added, and the mixture was mechanically stirred at 300 rpm. The reaction was carried out at 80 °C for 3 h. The NCO% titration reached the theoretical value. Then, 0.65 g (5 mmol) of hydroxyethyl methacrylate and 2.62 g of dipentaerythritol pentaacrylate were added dropwise as end-capping agents, along with 0.1% 4-methoxyphenol. The reaction was carried out at 70 °C for 4 h. The reaction ended when the NCO% titration was ≤0.06%, yielding a fluorinated polyurethane acrylate oligomer with the following structure:

[0138]

[0139] Where R c and R d The structure is as follows:

[0140]

[0141] The modified silica sol preparation process includes the following steps:

[0142] 10.4 g (0.05 mol) of tetraethyl orthosilicate and 6.9 g (0.15 mol) of anhydrous ethanol were added to a three-necked flask, heated to 40 °C, and stirred for 15 min at 500 rpm. Then, an acid solution consisting of 0.062 ml of hydrochloric acid and 3.15 g (0.175 mol) of deionized water was added dropwise, and the mixture was stirred for 2 h. Subsequently, 9.17 g (0.05 mol) of (3-mercaptopropyl)trimethoxysilane was added dropwise, and the mixture was heated to 60 °C and reacted for 6 h. The mixture was then discharged and aged for 4 days to obtain a modified silica sol, the structure of which is as follows.

[0143]

[0144] Among them M and M 5 The structure is as follows

[0145]

[0146] Example 6

[0147] (1) Clean the surface of the glass slide thoroughly and dry it for later use;

[0148] (2) Add 0.5g (12.92%) 1,6-hexanediol diacrylate and 0.75g (19.38%) modified silica sol to 2.5g (64.60%) fluorinated polyurethane acrylate oligomer and let stand in a container for 30min. Add 0.1g (2.6%) photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine, 0.01g (0.25%) leveling agent BYK-3550 and 0.01g (0.25%) defoamer BYK-066N to the container and stir magnetically in the dark until homogeneous and transparent to obtain a mixed coating.

[0149] (3) Apply the mixed coating to the cleaned glass slide with a thickness of 30±1 μm.

[0150] (4) Place the coated substrate under a UV-LED lamp for 90 seconds to obtain a transparent coating.

[0151] The preparation process of fluorinated polyurethane acrylate oligomers includes the following steps:

[0152] Under a nitrogen atmosphere, 0.3 g (0.5 mmol) of perfluoropolyether diol FD-162 (Mn = 600 g / mol), 9 g (4.5 mmol) of dehydrated polycarbonate diol MNF3230 (Mn = 2000 g / mol), and 2.24 g (10 mmol) of isophorone diisocyanate were sequentially added to a three-necked flask. 0.3% dibutyltin dilaurate was added, and the mixture was mechanically stirred at 300 rpm. The reaction was carried out at 80 °C for 3 h. The NCO% titration reached the theoretical value. Then, 2.62 g (5 mmol) of dipentaerythritol pentaacrylate and 1.49 g (5 mmol) of pentaerythritol triacrylate were added dropwise as end-capping agents, along with 0.05% 2,6-di-tert-butyl-p-methylphenol. The reaction was carried out at 70 °C for 4 h. The reaction ended when the NCO% titration was ≤0.06%, yielding a fluorinated polyurethane acrylate oligomer with the following structure:

[0153]

[0154] Where R e and R f The structure is as follows:

[0155]

[0156] The modified silica sol preparation process includes the following steps:

[0157] 10.4 g (0.05 mol) of tetraethyl orthosilicate and 6.9 g (0.15 mol) of anhydrous ethanol were added to a three-necked flask, heated to 40 °C, and stirred for 15 min at 500 rpm. Then, an acid solution consisting of 0.062 mL of hydrochloric acid and 3.15 g (0.175 mol) of deionized water was added dropwise, and the mixture was stirred for 2 h. Subsequently, 6.10 g (0.01 mol) of perfluorodecyltriethoxysilane was added dropwise, and the mixture was heated to 60 °C and reacted for 6 h. The mixture was then discharged and aged for 4 days to obtain a modified silica sol, the structure of which is as follows.

[0158]

[0159] Among them M and M 6 The structure is as follows

[0160]

[0161] Comparative Example 1

[0162] (1) Clean the surface of the glass slide thoroughly and dry it for later use;

[0163] (2) Add 0.5g (16.03%) of 1,6-hexanediol diacrylate to 2.5g (80.13%) of fluorinated polyurethane acrylate oligomer and let stand in a container for 30min. Add 0.1g (3.2%) of photoinitiator 1-hydroxycyclohexylphenyl ketone, 0.01g (0.32%) of leveling agent BYK333 and 0.01g (0.32%) of defoamer AFE-1430 to the container and stir magnetically in the dark until homogeneous and transparent to obtain a mixed coating.

[0164] (3) Apply the mixed coating to the cleaned glass slide with a thickness of 30±1um;

[0165] (4) Place the coated substrate under a UV-LED lamp for 90 seconds to obtain a transparent coating.

[0166] The preparation process of fluorinated polyurethane acrylate oligomers includes the following steps:

[0167] Under a nitrogen atmosphere, 0.3 g (0.5 mmol) of perfluoropolyether diol FD-162 (Mn = 600 g / mol), 9 g (4.5 mmol) of dehydrated polycarbonate diol UH-200 (Mn = 2000 g / mol), and 2.24 g (10 mmol) of isophorone diisocyanate were added sequentially to a three-necked flask, followed by the addition of 0.3% dibutyltin dilaurate. The mixture was mechanically stirred at 300 rpm and reacted at 80 °C for 3 h. The NCO% titration was performed until the theoretical value was reached. Then, 1.3 g (10 mmol) of the end-capping agent hydroxyethyl methacrylate and 0.1% hydroquinone were added dropwise, and the reaction was carried out at 70 °C for 4 h. The reaction was terminated when the NCO% titration was ≤ 0.06%, yielding a fluorinated polyurethane acrylate oligomer.

[0168] The structural formula of the fluorinated polyurethane acrylate oligomer is the same as that in Example 1.

[0169] Comparative Example 2

[0170] (1) Clean the surface of the glass slide thoroughly and dry it for later use;

[0171] (2) Add 1.0g (16%) trimethylolpropane triacrylate to 5.0g (80%) fluorinated polyurethane acrylate oligomer and let stand in a container for 30min. Add 0.21g (3.4%) photoinitiator benzoin diethyl ether, 0.02g (0.3%) leveling agent BYK-3550 and 0.01g (0.2%) defoamer BYK-066N to the container and stir magnetically in the dark until homogeneous and transparent to obtain a mixed coating.

[0172] (3) Apply the mixed coating to the cleaned glass slide with a thickness of 30±1um;

[0173] (4) Place the coated substrate under a UV-LED lamp for 90 seconds to obtain a transparent coating.

[0174] The preparation process of fluorinated polyurethane acrylate oligomers includes the following steps:

[0175] Under a nitrogen atmosphere, 1.0 g (0.5 mmol) of perfluoropolyether diol FD-164 (Mn = 2000 g / mol), 9 g (4.5 mmol) of dehydrated polycarbonate diol PH-200 (Mn = 2000 g / mol), and 2.24 g (10 mmol) of isophorone diisocyanate were added sequentially to a three-necked flask. 0.3% dibutyltin dilaurate was added, and the mixture was mechanically stirred at 300 rpm. The reaction was carried out at 80 °C for 3 h. The NCO% titration reached the theoretical value. Then, 2.98 g (10 mmol) of pentaerythritol triacrylate (the end-capping agent) and 0.05% 4-methoxyphenol were added dropwise. The reaction was carried out at 70 °C for 4 h. The reaction ended when the NCO% titration was ≤0.06%, yielding a fluorinated polyurethane acrylate oligomer.

[0176] The structural formula of the fluoropolyurethane acrylate oligomer is the same as in Example 2.

[0177] Comparative Example 3

[0178] (1) Clean the surface of the glass slide thoroughly and dry it for later use;

[0179] (2) Add 1.0g (14.86%) of acrylate isoborneol ester and 0.5g (7.43%) of modified silica sol to 5.0g (74.29%) of fluorinated polyurethane acrylate oligomer and let stand in a container for 30min. Add 0.20g (2.97%) of photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone, 0.01g (0.15%) of leveling agent BYK-3455 and 0.02g (0.3%) of defoamer AT-99 to the container and stir magnetically in the dark until homogeneous and transparent to obtain a mixed coating.

[0180] (3) Apply the mixed coating to the cleaned glass slide with a thickness of 30±1um;

[0181] (4) Place the coated substrate under a UV-LED lamp for 90 seconds to obtain a transparent coating.

[0182] The preparation process of fluorinated polyurethane acrylate oligomers includes the following steps:

[0183] Under a nitrogen atmosphere, 0.65 g (0.5 mmol) of perfluoropolyether diol FD-163 (Mn = 1300 g / mol), 9 g (4.5 mmol) of dehydrated polycarbonate diol BH-200 (Mn = 2000 g / mol), and 2.24 g (10 mmol) of isophorone diisocyanate were sequentially added to a three-necked flask, followed by the addition of 0.3% dibutyltin dilaurate and mechanical stirring at 300 rpm. The reaction was carried out at 80 °C for 3 h, and the NCO% was titrated to reach the theoretical value. Then, 5.24 g (10 mmol) of dipentaerythritol pentaacrylate as a capping agent and 0.1% of 2,6-di-tert-butyl-p-methylphenol were added dropwise, and the reaction was carried out at 70 °C for 4 h. The reaction ended when the NCO% titrated to ≤0.06%, yielding a fluorinated polyurethane acrylate oligomer.

[0184] The structural formula of the fluorinated polyurethane acrylate oligomer is the same as that in Example 3.

[0185] Comparative Example 4

[0186] (1) Clean the surface of the glass slide thoroughly and dry it for later use;

[0187] (2) Add 0.5g (16.03%) diethylene glycol diacrylate to 2.5g (80.13%) fluorinated polyurethane acrylate oligomer and let stand in a container for 30min. Add 0.1g (3.2%) photoinitiator 2-hydroxy-4-(2-hydroxyethoxy)-2-methylphenylacetone, 0.01g (0.32%) leveling agent BYK333 and 0.01g (0.32%) defoamer AS-6800 to the container and stir magnetically in the dark until homogeneous and transparent to obtain a mixed coating.

[0188] (3) Apply the mixed coating to the cleaned glass slide with a thickness of 30±1um;

[0189] (4) Place the coated substrate under a UV-LED lamp for 90 seconds to obtain a transparent coating.

[0190] The preparation process of fluorinated polyurethane acrylate oligomers includes the following steps:

[0191] Under a nitrogen atmosphere, 0.52 g (0.5 mmol) of perfluoropolyether diol (Wuhan Lana White 1937, Mn = 1040 g / mol), 9 g (4.5 mmol) of dehydrated polycarbonate diol (G3452, Mn = 2000 g / mol), and 2.24 g (10 mmol) of isophorone diisocyanate were sequentially added to a three-necked flask. 0.3% dibutyltin dilaurate was added, and the mixture was mechanically stirred at 300 rpm. The reaction was carried out at 80 °C for 3 h. The NCO% titration reached the theoretical value. Then, 0.65 g (5 mmol) of hydroxyethyl methacrylate and 1.49 g (5 mmol) of pentaerythritol triacrylate were added dropwise as end-capping agents, along with 0.05% hydroquinone. The reaction was carried out at 70 °C for 4 h. The reaction ended when the NCO% titration was ≤0.06%, yielding a fluorinated polyurethane acrylate oligomer.

[0192] The structural formula of the fluorinated polyurethane acrylate oligomer is the same as that in Example 4.

[0193] Comparative Example 5

[0194] (1) Clean the surface of the glass slide thoroughly and dry it for later use;

[0195] (2) Add 1.0g (16.31%) dicyclopentenyl acrylate to 5.0g (81.57%) fluorinated polyurethane acrylate oligomer and let stand in a container for 30min. Add 0.1g (1.63%) photoinitiator ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 0.01g (0.16%) leveling agent BYK-3455 and 0.02g (0.33%) defoamer AFE-1430 to the container and stir magnetically in the dark until homogeneous and transparent to obtain a mixed coating.

[0196] (3) Apply the mixed coating to the cleaned glass slide with a thickness of 30±1 μm.

[0197] (4) Place the coated substrate under a UV-LED lamp for 90 seconds to obtain a transparent coating.

[0198] The preparation process of fluorinated polyurethane acrylate oligomers includes the following steps:

[0199] Under a nitrogen atmosphere, 0.65 g (0.5 mmol) of perfluoropolyether diol FD-163 (Mn = 1300 g / mol), 9 g (4.5 mmol) of dehydrated polycarbonate diol PC06349 (Mn = 2000 g / mol), and 2.24 g (10 mmol) of isophorone diisocyanate were sequentially added to a three-necked flask, and 0.3% dibutyltin dilaurate was added. The mixture was mechanically stirred at 300 rpm and reacted at 80 °C for 3 h. The NCO% was titrated to reach the theoretical value. Then, 0.65 g (5 mmol) of hydroxyethyl methacrylate and 2.62 g of dipentaerythritol pentaacrylate were added dropwise as end-capping agents, along with 0.1% 4-methoxyphenol. The reaction was carried out at 70 °C for 4 h. The reaction ended when the NCO% titration was ≤0.06%, yielding a fluorinated polyurethane acrylate oligomer.

[0200] The structural formula of the fluorinated polyurethane acrylate oligomer is the same as that in Example 5.

[0201] Comparative Example 6

[0202] (1) Clean the surface of the glass slide thoroughly and dry it for later use;

[0203] (2) Add 0.5g (16.03%) of 1,6-hexanediol diacrylate to 2.5g (80.13%) of fluorinated polyurethane acrylate oligomer and let stand in a container for 30min. Add 0.1g (3.2%) of photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine, 0.01g (0.32%) of leveling agent BYK-3550 and 0.01g (0.32%) of defoamer BYK-066N to the container and stir magnetically in the dark until homogeneous and transparent to obtain a mixed coating.

[0204] (3) Apply the mixed coating to the cleaned glass slide with a thickness of 30±1 μm.

[0205] (4) Place the coated substrate under a UV-LED lamp for 90 seconds to obtain a transparent coating.

[0206] The preparation process of fluorinated polyurethane acrylate oligomers includes the following steps:

[0207] Under a nitrogen atmosphere, 0.3 g (0.5 mmol) of perfluoropolyether diol FD-162 (Mn = 600 g / mol), 9 g (4.5 mmol) of dehydrated polycarbonate diol MNF3230 (Mn = 2000 g / mol), and 2.24 g (10 mmol) of isophorone diisocyanate were sequentially added to a three-necked flask, followed by the addition of 0.3% dibutyltin dilaurate and mechanical stirring at 300 rpm. The reaction was carried out at 80 °C for 3 h, and the NCO% was titrated to reach the theoretical value. Then, 2.62 g (5 mmol) of dipentaerythritol pentaacrylate and 1.49 g (5 mmol) of pentaerythritol triacrylate were added dropwise as end-capping agents, along with 0.05% of 2,6-di-tert-butyl-p-methylphenol. The reaction was carried out at 70 °C for 4 h, and the reaction was terminated when the NCO% titrated to ≤0.06%, yielding a fluorinated polyurethane acrylate oligomer.

[0208] The structural formula of the fluorinated polyurethane acrylate oligomer is the same as that in Example 6.

[0209] The properties of different hybrid coatings obtained from various embodiments and comparative examples of the present invention are shown in Table 1.

[0210] Table 1. Coating film performance test results for the examples and comparative examples.

[0211]

[0212]

[0213] Note: Coating hardness was tested according to GB / T 6739-2006, using a Mitsubishi pencil with a load of 750g; coating adhesion was tested according to GB / T 9286-1998; the coating contact angle test involved placing the coating sample on a contact angle measuring instrument (model: JC2000D2, provided by Shanghai Zhongchen Digital Technology Equipment Co., Ltd.), and at room temperature, dropping 5μL of deionized water onto the sample surface using a quantitative sampler. Each sample was measured five times, and the average value was taken as the contact angle of that sample; severe scratches on the paint film appearance were represented by "×", minor scratches or no scratches were represented by "√"; "None" water contact angle indicated that the coating had been completely scratched.

[0214] As shown in Table 1, adding modified silica sol to the matrix resin greatly improves the hardness and wear resistance of the coating and slightly improves its hydrophobicity, but adding too much will also affect the coating performance.

[0215] Table 2. Anti-fingerprint properties of the coatings prepared in Examples 1-6 and Comparative Examples 1-6

[0216]

[0217]

[0218] The addition of modified silica sol makes the coating denser, making fingerprints easier to remove and improving the coating's anti-fingerprint performance. Anti-fingerprint performance test: The artificial fingerprint liquid consists of 95% artificial sweat and 5% artificial sebum. The artificial sweat is prepared by mixing 3 mL / L lactic acid, 5 mL / L acetic acid, 10 g / L sodium chloride, 10 g / L sodium hydrogen phosphate, and deionized water. The artificial sebum consists of oleic acid (2%), stearic acid (2%), and squalene (1%). A small amount of nonionic surfactant (Triton X-100, 2 μL / g mixture) is added after mixing the artificial sweat and sebum to overcome the natural immiscibility between sweat and sebum. First, fingers are cleaned with alcohol, then immersed in the artificial fingerprint liquid, and then the surface of the coating is touched to form a fingerprint. The fingerprint is then wiped with a paper towel at a speed of 3 cm / s under a 500g load pressure. The number of wipings required to remove the fingerprint is recorded, and the results are shown in Table 2.

[0219] Table 3. Transmittance at 550 nm for Examples 1-6 and Comparative Examples 1-6

[0220]

[0221]

[0222] As shown in Table 3, the addition of modified silica sol enhances the transparency of the coating in the visible light region. The transmittance of the coating was tested using a UV spectrophotometer. According to GB / T 2680-1994, the transmittance of 12 groups of coating samples at 550 nm was tested respectively.

[0223] As can be seen from the above embodiments, this invention provides a UV-curable organic / inorganic hybrid low-fluorine wear-resistant and fingerprint-resistant coating and its preparation method. The innovation of this invention lies in using perfluorinated polyether glycol to modify polycarbonate glycol, synthesizing a novel fluorinated polyurethane acrylate resin, which effectively improves the coating's wear resistance, fingerprint resistance, and transparency. Simultaneously, a sol-gel technique is used to prepare modified silica particles that are compatible with the UV-curable resin system, improving the compatibility between the silica particles and the UV-curable resin system. The resulting hybrid UV coating has low inorganic components and low fluorine content, exhibiting high transparency, high hardness, high wear resistance, and excellent fingerprint resistance. Its water contact angle is greater than 110°, light transmittance is greater than 90%, and it retains its hydrophobicity even after 2000 cycles of steel wool rubbing; fingerprints can be removed with less than one wipe using a paper towel.

[0224] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A UV-cured organic / inorganic hybrid low-fluorine-containing abrasion-resistant anti-fingerprint coating, characterized in that, Prepared from raw materials including the following mass percentages: Fluorine-containing polyurethane acrylate oligomer 30~74.29%; Active diluent 10~30%; Modified silica sol 1~30%; Photoinitiator 1~4%; Leveling agent 0.1~0.5%; Defoaming agent 0.1~0.5%; The preparation method of the fluorine-containing polyurethane acrylate oligomer includes the following steps: S1, under N2 environment, mix perfluoropolyether diol, polycarbonate diol, diisocyanate and organic metal catalyst, and then react to obtain NCO-terminated prepolymer; S2, add polymerization inhibitor and end-capping agent monomer to the above prepolymer to react to obtain fluorine-containing polyurethane acrylate resin; The molar ratio of the perfluoropolyether diol and the polycarbonate diol is 1:5~10; the molar ratio of the polycarbonate diol and the diisocyanate is 1:1~2, and the amount of the organic metal catalyst is 0.1~2% of the total mass of the perfluoropolyether diol, the polycarbonate diol and the diisocyanate; The amount of the polymerization inhibitor is 0.01~0.1% of the mass of the prepolymer, and the molar ratio of the diisocyanate and the end-capping agent monomer is 2:1~2.

2. The UV-cured organic / inorganic hybrid low-fluorine-containing abrasion-resistant anti-fingerprint coating according to claim 1, characterized in that, The perfluoropolyether diol contains one or more of Italian SOLVAY FLUOROLINK D 4000, domestic Yu'ao Huihong FD-162, FD-163, FD-164 and domestic Wuhan Lanya white goods No. 1937; The polycarbonate diol contains one or more of UH-200, PH-200 and BH-200 in the Yubaru PCDL series, Asahi Kasei G3452, G3450J, T4672, T4692, T4691 and T5652, and Kolon C-2050 and C-2090, and domestic Guangdong Wengjiang PC06349 and Muna Phi MNF3230; The diisocyanate contains one or more of isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate and hexamethylene diisocyanate; and the organic metal catalyst contains one or more of dibutyltin dilaurate, stannous octoate and organic bismuth.

3. The UV-cured organic / inorganic hybrid low-fluorine-containing abrasion-resistant anti-fingerprint coating according to claim 1 or 2, characterized in that, The polymerization inhibitor contains one or more of 4-methoxyphenol, hydroquinone and 2,6-di-tert-butyl-p-methylphenol; and the end-capping agent monomer contains one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, 2-ethoxyethyl acrylate, 2-cyanoacrylate, beta-hydroxypropyl acrylate, beta-hydroxypropyl methacrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

4. The UV-cured organic / inorganic hybrid low-fluorine-containing abrasion-resistant anti-fingerprint coating according to claim 2, characterized in that, In the step S1, the reaction temperature is 70~90℃, and the reaction time is 2~4h; in the step S2, the reaction temperature is 60~80℃, and the reaction time is 3~5h.

5. The UV-cured organic / inorganic hybrid low-fluorine-containing abrasion-resistant anti-fingerprint coating according to claim 1 or 4, characterized in that, The preparation method of the modified silica sol includes the following steps: S3, mix tetraethyl orthosilicate and anhydrous ethanol at 20~40℃, stir and heat, after reaching the reaction temperature, add hydrochloric acid solution catalyst to adjust pH=3~4, continue to react for a certain time after the end of dropwise addition, and obtain a hydrolysis solution; S4, adding different functional group silane into the hydrolysis solution to react, and aging to obtain modified silica sol; In the step S3, the mixing time is 15-30 min, the reaction temperature is 30-50℃, and the continuous reaction time is 2-3 h; in the step S4, the reaction temperature is 50-70℃, the reaction time is 4-8 h, and the aging time is 3-5 days.

6. The UV-cured organic / inorganic hybrid low-fluorine-containing abrasion-resistant anti-fingerprint coating according to claim 5, characterized in that, The molar ratio of the tetraethyl orthosilicate, the different functional group silane and the anhydrous ethanol is 1:0.1-5:1-10; the silane comprises one or more of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, methacryloyloxypropyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, perfluorodecyltriethoxysilane, (3-mercaptopropyl)trimethoxysilane, tridecafluoro-1-octyltrimethoxysilane, perfluoro polyether trimethoxysilane, dodecyltrimethoxysilane and dodecyltriethoxysilane.

7. The UV-cured organic / inorganic hybrid low-fluorine-containing abrasion-resistant anti-fingerprint coating according to claim 1 or 4 or 6, characterized in that, The reactive diluent comprises one or more of isobornyl acrylate, dicyclopentenyl acrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate and trimethylolpropane triacrylate; The photoinitiator comprises one or more of 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, 2-hydroxy-2-methyl-1-phenylpropanone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and 2,4,6-trimethylbenzoyl phenyl phosphonic acid ethyl ester; the leveling agent comprises one or more of Germany BYK-3455, BYK-3550 and BYK333; and the defoaming agent comprises one or more of American Dow AFE-1430, Germany BYK-066N, homemade Datian AT-99 and AS-6800.

8. The UV-cured organic / inorganic hybrid low-fluorine abrasion-resistant coating according to any one of claims 1 to 7. The preparation method of the anti-fingerprint coating is characterized by comprising the following steps: Mixing the fluorine-containing polyurethane acrylate oligomer, the reactive diluent, the modified silica sol, the photoinitiator, the leveling agent and the defoaming agent, avoiding light, standing and stirring to be homogeneous and transparent to obtain a sample; After the sample is coated on the surface of a dry substrate and is cured by ultraviolet light, a UV-cured organic / inorganic hybrid low-fluorine wear-resistant anti-fingerprint coating is obtained.

9. The production method according to claim 8, characterized by, The ultraviolet light curing time is 30-300 s.

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