An EB / excimer lamp-cured antifouling composition

Abstract

The present invention belongs to the field of functional coatings, and specifically relates to an EB / excimer lamp curing antifouling composition and a preparation method thereof, wherein the EB / excimer lamp curing antifouling composition comprises the following raw materials in parts by weight: 70-80 parts of polyurethane acrylate resin, 10-20 parts of acrylate monomer, 10-15 parts of functional modifier I, 5-10 parts of functional modifier II, 0-5.0 parts of color paste, 0-0.5 parts of dispersant, 0.1-0.5 parts of defoamer, 0.2-0.5 parts of leveling agent, and the EB / excimer lamp curing antifouling composition is obtained by high-speed dispersion and filtration. The EB / excimer lamp curing antifouling composition of the present invention is designed by formula, and cooperates with homemade functional modifier I and functional modifier II, which can effectively improve the anti-fingerprint property, insufficient continuous antifouling property and the defect of requiring additional addition of matting agent to achieve matte of the existing EB curing antifouling composition coating in the prior art, and has the properties of scratch resistance and the like.

Description

Technical Field

[0001] The invention belongs to the field of functional coatings, and in particular relates to an EB / excimer lamp-cured antifouling composition. Background Art

[0002] With the continuous progress of science and technology and the continuous improvement of people's living standards, people's demand for spiritual life is also getting higher and higher. This requires that products must not only meet people's basic material functional requirements, but also meet people's pursuit and yearning for spiritual life. Matt, anti-fingerprint, and anti-fouling materials can be achieved through surface coating technology. Surface coating technology can not only change the appearance of the material, but also improve the physical and chemical properties of the surface. Through surface coating technology, with the right functional modifier, the chemical resistance, scratch resistance, and antibacterial properties of the substrate can be significantly improved. Coatings have become the most widely used surface coating technology.

[0003] From the perspective of coating curing methods, it can be obtained by thermal curing or radiation. Compared with thermal curing, radiation curing technology is more in line with market development prospects. Radiation methods include ultraviolet (UV) and electron beam (EB) irradiation. Radiation methods have a fast curing speed and are emerging coating curing methods. Compared with UV curing, EB curing has the following advantages: high utilization rate of electrical energy; faster curing speed; EB has large energy, which is enough to directly open acrylates, generate free radicals, and initiate polymerization reactions, so no initiator is required, which improves the storage stability of the coating and reduces the color and odor caused by the byproducts produced by the decomposition of the photoinitiator; EB has strong penetration ability, which can reach up to several centimeters, while UV curing can only penetrate a thickness of tens of microns; EB does not need to consider the influence of colored systems, especially dark systems, while UV curing needs to avoid the absorption wavelength window of pigments and photoinitiators. In addition, a new excimer lamp technology has emerged in recent years, but its light penetration under high energy can only reach 0.1 microns, and it has no value for use alone.

[0004] On the other hand, the composition of the coating is crucial to its anti-fouling performance. Most organic coatings on the market currently usually add fluorine-containing or silicon-containing additives to improve their anti-fouling properties. These additives reduce the surface tension of the coating surface, making it difficult for liquids such as water and oil to spread on the coating surface, thereby improving the anti-fouling properties of the coating. However, during the use of the coating, especially when subjected to long-term friction, the anti-fouling properties of these additives may drop sharply. This is because friction may cause uneven distribution or wear of the additives on the coating surface, which reduces the anti-fouling properties of the coating surface, making it easy to adhere to fingerprints and other contaminants; in addition, in the process of preparing matte paint, a common method is to add a large amount of matting powder to the coating. As an insoluble solid particle, matting powder can scatter light, thereby reducing the gloss of the coating surface and achieving a matte effect. However, excessive matting powder may deteriorate the overall performance of the coating. This is because the matting powder particles may affect the rheological properties of the coating, resulting in uneven coating during construction. At the same time, the addition of matting powder may also reduce the performance of the coating. Summary of the invention

[0005] The purpose of the present invention is to address the defects of the existing EB radiation antifouling composition coating, such as insufficient anti-fingerprint and continuous antifouling properties, and the need to add a matte agent to achieve a matte finish. Through formula design, homemade functional modifier I and functional modifier II, combined with 172nm excimer lamp curing and EB curing technology, an EB / excimer lamp curing antifouling composition and a preparation method thereof are provided.

[0006] The present invention provides a functional modifier I for an EB / excimer lamp-cured antifouling composition, and a preparation method thereof comprises the following steps:

[0007] (1) subjecting trimethylolpropane and perfluorooctanoyl chloride to an esterification reaction under the action of an acid-binding agent, triethylamine, to obtain an intermediate product I;

[0008] (2) subjecting the intermediate product I and isocyanoethyl methacrylate to a nucleophilic addition reaction in the presence of a polymerization inhibitor, p-hydroxyanisole, and a catalyst, dibutyltin dilaurate, to obtain a mixed solution containing the intermediate product II;

[0009] (3) adding an asymmetric diisocyanate to the mixed solution containing the intermediate product II to carry out an affinity addition reaction to obtain a solution containing the intermediate product III;

[0010] (4) Adding hydroxychloroacetic acid resin to the solution containing the intermediate product III to cause affinity addition reaction to obtain the target product IV, i.e., the functional modifier I.

[0011] Furthermore, the usage ratio of trimethylolpropane, triethylamine and perfluorooctanoyl chloride is 1 mol: 1.0-1.1 mol: 1.0-1.1 mol.

[0012] Further, the usage ratio of the intermediate product I to isocyanoethyl methacrylate is 1 mol:1.1 mol;

[0013] The dosage of the polymerization inhibitor p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate;

[0014] The amount of the catalyst dibutyltin dilaurate used is 1wt% of the total mass of the reactants.

[0015] Furthermore, the asymmetric diisocyanate is toluene diisocyanate or isophorone diisocyanate.

[0016] Furthermore, the usage ratio of the asymmetric diisocyanate to the intermediate product I is 1.1 mol:1 mol.

[0017] Furthermore, the usage ratio of the hydroxychloroacetic acid resin to the asymmetric diisocyanate is 1 g:1.36 mmol.

[0018] The present invention also provides a functional modifier I for an EB / excimer lamp-cured antifouling composition.

[0019] The present invention provides a functional modifier II for an EB / excimer lamp-cured antifouling composition, and the preparation method thereof is as follows:

[0020] Nano-SiO 2 The target product, namely, functional modifier II, is obtained by coupling reaction with a silane coupling agent.

[0021] Furthermore, the silane coupling agent is a silane coupling agent containing a carbon-carbon double bond or a silane coupling agent containing a mercapto group.

[0022] Furthermore, the nano-SiO 2 The dosage ratio of silane coupling agent and deionized water is: 5.00g:35.00g:1.00g.

[0023] The present invention also provides a functional modifier II for the EB / excimer lamp-cured antifouling composition.

[0024] The present invention also provides an EB / excimer lamp curing antifouling composition, comprising the following raw materials in parts by weight:

[0025] Polyurethane acrylate resin 70-80 parts;

[0026] Acrylate monomer 10-20 parts;

[0027] Functional modifier I 10-15 parts;

[0028] Functional modifier II 5-10 parts;

[0029] Color paste 0-5.0 parts;

[0030] Dispersant 0-0.5 parts;

[0031] Defoaming agent 0.1-0.5 parts;

[0032] 0.2-0.5 parts of leveling agent.

[0033] The present invention also provides a method for preparing an EB / excimer lamp-cured antifouling composition, comprising the following steps:

[0034] Protect from light, keep humidity ≤60%, mix polyurethane acrylate resin, acrylate monomer, functional modifier I, functional modifier II, color paste, dispersant, defoamer and leveling agent according to the formula ratio, stir at a speed of 2000r / min for 30min, and obtain an EB / excimer lamp curing antifouling composition.

[0035] The present invention also provides a method for preparing an EB-cured antifouling coating, comprising the following steps:

[0036] S1: The EB / excimer lamp curing antifouling composition is uniformly coated on the substrate, preheated at 60° C. for 5 min, and placed under a 172 nm excimer lamp for excimer lamp curing;

[0037] S2: The coating obtained in S1 is subjected to EB curing to obtain an EB-cured anti-fouling coating.

[0038] Furthermore, the energy density of the excimer lamp is 1000-5000 mW / cm 2 , radiation time 2-10s, oxygen content 5-200ppm.

[0039] Furthermore, the EB curing has a radiation dose of 100-200 kGy and a radiation time of 2-5 s.

[0040] The present invention has the following beneficial effects:

[0041] (1) The present invention provides an EB / excimer lamp-cured antifouling composition, wherein the main resin is a polyurethane acrylate resin. On the one hand, the acrylate with a polyurethane structure has excellent adhesion to commonly used substrates such as PVC, PC, and PMMA; on the other hand, the polyurethane structure has excellent wear resistance.

[0042] (2) The present invention provides an EB / excimer lamp curing antifouling composition, wherein one of its components, a functional modifier I, contains a chlorovinyl structure, a polyurethane, a F element, an acryloyloxy group and other structures in its molecular structure. First, the chlorovinyl resin structure has excellent dispersibility for high-color fillers, giving it superiority in the application field of high-color fillers; second, a multifunctional acryloyloxy structure is formed with the chlorovinyl resin molecular chain as the main chain, giving it the function of a crosslinking agent; third, the presence of the polyurethane structure ensures excellent compatibility with the main resin, thereby improving mechanical properties, etc.; fourth, the presence of a large amount of fluorine elements, due to the low surface tension of F, can enrich the functional modifier I on the surface, giving the coating surface a hydrophobic antifouling effect; fifth, due to the synergistic effect of the chlorovinyl resin and the polyurethane structure, the modifier I can be enriched on the coating surface, which not only improves the hydrophobicity of the coating, but also significantly reduces the adhesion of fingerprint oil stains, thereby providing excellent anti-fingerprint performance.

[0043] (3) The present invention provides an EB / excimer lamp curing antifouling composition, one of the components of which is a functional modifier II, which is a silane-modified nano-silica structure. First, the presence of Si element can further improve the hydrophobic antifouling effect of the coating surface; second, nano-silica can improve the scratch resistance of the coating surface; third, the surface of the silane-modified nano-silica gathers a large number of thiol groups or carbon-carbon double bonds, which can act as a multifunctional cross-linking agent to improve surface properties (such as hydrophobicity, scratch resistance, etc.).

[0044] (4) The present invention provides an EB / excimer lamp curing antifouling composition, which is used in combination with excimer lamp curing and EB curing technology. First, a 172nm excimer lamp is used to cure the surface layer of the coating under the protection of an inert gas. First, the 172nm short-wave ultraviolet light has high energy and can directly initiate a free radical polymerization reaction without the need to add a photoinitiator; but the penetration depth is low, <0.1um, and polymerization reactions within 0.1um of the outermost layer can be achieved. When the shrinkage stress generated by the curing of the surface layer is large, and the bottom layer does not have time to move, wrinkles are formed to achieve a matte effect; second, because the surface layer is enriched with a large amount of functional modifier I and functional modifier II, it is a multi-functional structure, and under the high energy of the 172nm excimer lamp, the wrinkled surface layer formed has higher hardness and scratch resistance; third, the surface layer is first cured with an excimer lamp, the surface layer is more fully cured, and the surface performance is better.

[0045] (5) The present invention provides an EB / excimer lamp curing antifouling composition, which is used in combination with excimer lamp curing and EB curing technology. EB is then used for complete curing. First, EB can form a certain degree of etching on the substrate, especially the polymer substrate, to improve the adhesion between the coating and the substrate; second, the excimer lamp is first used to cure the surface in an inert gas drop, and then EB curing is performed, without the need for inert gas, which is energy-saving. DETAILED DESCRIPTION

[0046] The present invention is described in detail below with reference to the examples. However, it should be understood that the following examples are only illustrative of the embodiments of the present invention, and are not intended to limit the scope of the present invention.

[0047] The embodiment of the present invention discloses an EB / excimer lamp curing antifouling composition, comprising the following raw materials in parts by weight:

[0048] Polyurethane acrylate resin 70-80 parts;

[0049] Acrylate monomer 10-20 parts;

[0050] Functional modifier I 10-15 parts;

[0051] Functional modifier II 5-10 parts;

[0052] Color paste 0-5.0 parts;

[0053] Dispersant 0-0.5 parts;

[0054] Defoaming agent 0.1-0.5 parts;

[0055] 0.2-0.5 parts of leveling agent.

[0056] The polyurethane acrylate resin in the present invention is a multifunctional resin, preferably trifunctional or above, to increase the degree of crosslinking after curing, including CN9010NS, CN9006NS, CN9110NS, CN970A60NS, CN971A80, CN8009NS, etc. from Sartomer.

[0057] The acrylate monomer in the present invention may be a monofunctional monomer, a difunctional monomer, or a multifunctional monomer, and the present application does not impose any particular limitation thereto.

[0058] The monofunctional monomer is preferably one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, isooctyl acrylate, dodecyl acrylate, octadecyl acrylate, isobornyl acrylate, caprolactone acrylate, 2-methoxyethyl acrylate, 2-butoxyethyl acrylate, 2-dimethylaminoethyl acrylate, ethoxyethoxyethyl acrylate, tetrahydrofuran methanol acrylate, phenoxyethyl acrylate, hexanediol methoxy monoacrylate, and ethoxylated neopentyl glycol methoxy monoacrylate.

[0059] The bifunctional acrylate monomer is preferably one or more of 1,3-propylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, cyclohexanedimethanol diacrylate, and ethoxylated bisphenol A diacrylate.

[0060] The multifunctional acrylate monomer is preferably one or more of trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane tetraacrylate, ethoxylated pentaerythritol tripropylene glycol ester, propoxylated pentaerythritol tripropylene glycol ester, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetrapropylene glycol ester, and propoxylated pentaerythritol tetrapropylene glycol ester.

[0061] The functional modifier I is prepared by the following method:

[0062] (1) dissolving trimethylolpropane and triethylamine in N,N-dimethylformamide A and placing them in a reaction container, dissolving perfluorooctanoyl chloride in N,N-dimethylformamide B and placing them in a constant pressure dropping funnel, placing them in an ice bath, stirring, and after the addition is completed, controlling the temperature to continue stirring at 0-5°C for 8-14 hours. After the reaction is completed, filtering, distilling under reduced pressure, dissolving the concentrate in dichloromethane A, adding saturated sodium bicarbonate solution to the solution, washing it 3 times, and then washing it with deionized water 3 times, separating the liquids, taking the organic phase, drying it with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure, and drying it in a vacuum at 80°C for 4 hours to obtain an intermediate product I;

[0063] The dosage ratio of trimethylolpropane, triethylamine, N,N-dimethylformamide A, perfluorooctanoyl chloride, N,N-dimethylformamide B, dichloromethane A, saturated sodium bicarbonate solution, deionized water, and anhydrous sodium sulfate is: 1 mol: 1.0-1.1 mol: 400 mL: 1.0-1.1 mol: 150 mL: 500 mL: 400 mL: 400 mL: 50 g;

[0064] (2) Dissolve the intermediate product I, dibutyltin dilaurate, and p-hydroxyanisole in N,N-dimethylformamide C and place them in a reaction container; dissolve isocyanoethyl methacrylate in N,N-dimethylformamide D and place them in a constant pressure dropping funnel; stir, dropwise add, and heat to 80-90° C.; continue stirring for 2-4 hours after the dropwise addition is completed, and let stand to obtain a mixed solution containing the intermediate product II;

[0065] The usage ratio of the intermediate product I, N,N-dimethylformamide C, isocyanoethyl methacrylate, and N,N-dimethylformamide D is: 1 mol: 300 mL: 1.1 mol: 200 mL;

[0066] The amount of dibutyltin dilaurate is 1wt% of the total mass of the reactants;

[0067] The dosage of the p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate;

[0068] (3) dissolving an asymmetric diisocyanate in N,N-dimethylformamide E in a reaction vessel, placing the mixed solution containing the intermediate product II in a constant pressure dropping funnel, stirring, dropping, heating to 60-90° C., continuing to stir for 2-4 hours after the dropwise addition, and standing to obtain a solution containing the intermediate product III;

[0069] The ratio of the amount of the asymmetric diisocyanate, N,N-dimethylformamide E and the amount of the intermediate product I is: 1.1 mol: 300 mL: 1 mol;

[0070] (4) Dissolve the hydroxychloroacetate resin in N,N-dimethylformamide F, add the solution to the intermediate product III, stir at 80-100° C. for 5-10 hours, cool to room temperature after the reaction, distill under reduced pressure, add methanol, take the precipitate, and dry it in vacuum at 40° C. for 24 hours to obtain the target product IV;

[0071] The usage ratio of the hydroxychloroacetic acid resin, N,N-dimethylformamide F and asymmetric diisocyanate is: 1 g: 30 mL: 1.36 mmol.

[0072] The asymmetric diisocyanate is toluene diisocyanate or isophorone diisocyanate.

[0073] The hydroxychloroacetic acid resin is UMOH or LPOH produced by Wuxi Honghui New Materials Technology Co., Ltd.

[0074] The functional modifier II is prepared by the following method:

[0075] Nano-SiO 2 Place in a reaction container filled with ethyl acetate A, ultrasonically disperse for 1 hour, add silane coupling agent and deionized water, slowly heat to 60-80°C, heat and stir for 6-14 hours; after the reaction, cool to room temperature, filter, wash with ethyl acetate B, and vacuum dry at 80°C to constant weight to obtain the target product;

[0076] The nano-SiO 2The usage ratio of ethyl acetate, silane coupling agent, deionized water, and ethyl acetate B is: 5.00g:200mL:35.00g:1.00g:600mL.

[0077] The silane coupling agent is a silane coupling agent containing a carbon-carbon double bond or a silane coupling agent containing a mercapto group.

[0078] The silane coupling agent containing a carbon-carbon double bond is preferably any one of γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, vinyltriethoxysilane, and vinyltri(β-methoxyethoxy)silane.

[0079] The mercapto group-containing silane coupling agent is preferably any one of 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane.

[0080] The nano silicon dioxide is from Shanghai Huijing Sub-Nano New Materials Co., Ltd., and has a particle size of 5-10 nm.

[0081] The color pastes described in the present invention are Thyssen FLUV-2700 (organic medium yellow), FLUV-6500 (color blue), and UV extra white.

[0082] The dispersant in the present invention is TEGO Dispers 670.

[0083] The defoamer in the present invention is BYK 1791.

[0084] The leveling agent in the present invention is DOWSIL 204SL.

[0085] The embodiment of the present invention also discloses a method for preparing an EB / excimer lamp-cured antifouling composition, comprising the following steps:

[0086] Protect from light, keep humidity ≤60%, mix polyurethane acrylate resin, acrylate monomer, functional modifier I, functional modifier II, color paste, dispersant, defoamer and leveling agent according to the formula ratio, stir at a speed of 2000r / min for 30min, and obtain an EB / excimer lamp curing antifouling composition.

[0087] The EB / excimer lamp-cured antifouling composition of the present invention has a viscosity of 100-300 cps, preferably 150-250 cps.

[0088] The embodiment of the present invention also discloses a method for preparing an EB-cured antifouling coating, comprising the following steps:

[0089] S1: The EB / excimer lamp curing antifouling composition is uniformly coated on the substrate, preheated at 60° C. for 5 min, and placed under a 172 nm excimer lamp for excimer lamp curing;

[0090] S2: The coating obtained in S1 is subjected to EB curing to obtain an EB-cured anti-fouling coating.

[0091] The energy density of the excimer lamp is 1000-5000 mW / cm 2 , can be 1000W / cm 2 , 1500W / cm 2 , 2000W / cm 2 , 2500W / cm 2 、3000W / cm 2 、3500W / cm 2 , 4000W / cm 2 、4500W / cm 2 , 5000W / cm 2 ; Radiation time 2-10s, can be 2s, 3s, 4s, 5s, 6s, 7s, 8s, 9s, 10s; oxygen content 5-200ppm, can be 5ppm, 10ppm, 20ppm, 50ppm, 80ppm, 100ppm, 120ppm, 150ppm, 200ppm.

[0092] The EB curing has a radiation dose of 100-200 kGy, which can be 100 kGy, 110 kGy, 120 kGy, 130 kGy, 140 kGy, 150 kGy, 160 kGy, 170 kGy, 180 kGy, 190 kGy, 200 kGy; and a radiation time of 2-5 s, which can be 2 s, 3 s, 4 s, or 5 s.

[0093] In order to further understand the present invention, the preparation method of the EB / excimer lamp-cured antifouling composition and coating provided by the present invention is described in detail below in conjunction with the examples. The protection scope of the present invention is not limited by the following examples.

[0094] Example 1

[0095] An EB / excimer lamp curing antifouling composition comprises the following raw materials in parts by weight:

[0096] Polyurethane acrylate resin CN970A60NS 80 parts;

[0097] 6 parts of isooctyl acrylate;

[0098] 1. 6 parts of 6-hexanediol diacrylate;

[0099] 3 parts of ethoxylated trimethylolpropane triacrylate;

[0100] Functional modifier I 12 parts;

[0101] Functional modifier II 8 parts;

[0102] Defoaming agent 0.1 part;

[0103] 0.2 parts of leveling agent.

[0104] The above functional modifier I is prepared by the following method:

[0105] (1) dissolving trimethylolpropane and triethylamine in N,N-dimethylformamide A in a reaction container, dissolving perfluorooctanoyl chloride in N,N-dimethylformamide B in a constant pressure dropping funnel, placing in an ice bath, stirring, and after the addition is completed, stirring is continued at 5° C. for 10 hours. After the reaction is completed, filtering, distilling under reduced pressure, dissolving the concentrate in dichloromethane A, adding saturated sodium bicarbonate solution to the solution, washing three times, and then washing with deionized water three times, separating the liquids, taking the organic phase, drying with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure, and drying under vacuum at 80° C. for 4 hours to obtain intermediate product I;

[0106] The dosage ratio of trimethylolpropane, triethylamine, N,N-dimethylformamide A, perfluorooctanoyl chloride, N,N-dimethylformamide B, dichloromethane A, saturated sodium bicarbonate solution, deionized water, and anhydrous sodium sulfate is: 1 mol: 1.1 mol: 400 mL: 1.1 mol: 150 mL: 500 mL: 400 mL: 400 mL: 50 g;

[0107] Its infrared data is as follows: 3538cm -1 :-OH exists; 1737cm -1 :-C=O exists; 1276cm -1 :-CF exists.

[0108] (2) Dissolve the intermediate product I, dibutyltin dilaurate, and p-hydroxyanisole in N,N-dimethylformamide C and place them in a reaction container; dissolve isocyanoethyl methacrylate in N,N-dimethylformamide D and place them in a constant pressure dropping funnel; stir, dropwise add, and heat to 90° C.; continue stirring for 3 h after the dropwise addition is completed, and let stand to obtain a mixed solution containing the intermediate product II;

[0109] The usage ratio of the intermediate product I, N,N-dimethylformamide C, isocyanoethyl methacrylate, and N,N-dimethylformamide D is: 1 mol: 300 mL: 1.1 mol: 200 mL;

[0110] The amount of dibutyltin dilaurate is 1wt% of the total mass of the reactants;

[0111] The dosage of the p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate;

[0112] Its infrared data is as follows: 3538cm -1 :-OH exists and weakens; 1737cm -1 :-C=O exists and is enhanced; 1276cm -1 :-CF exists; 3350cm -1 、1720cm -1 : Carbamate exists; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO does not exist.

[0113] (3) Dissolve toluene diisocyanate in N,N-dimethylformamide E and place it in a reaction container. Place the mixed solution containing the intermediate product II in a constant pressure dropping funnel, stir, add dropwise, and heat to 60° C. After the addition is completed, continue stirring for 3 hours and let stand to obtain a solution containing the intermediate product III;

[0114] The ratio of the amount of toluene diisocyanate, N,N-dimethylformamide E to the amount of the intermediate product I is: 1.1 mol: 300 mL: 1 mol;

[0115] Its infrared data is as follows: 3538cm -1 :-OH disappears; 1737cm -1 :-C=O exists; 1276cm -1 :-CF exists; 3350cm -1 、1720cm -1 : Carbamate exists and is enhanced; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO exists.

[0116] (4) Dissolve the hydroxychloroacetic acid resin in N,N-dimethylformamide F, add the solution to the intermediate product III, stir at 80°C for 6 hours, cool to room temperature after the reaction, distill under reduced pressure, add methanol, take the precipitate, and dry it in vacuum at 40°C for 24 hours to obtain the target product IV;

[0117] The dosage ratio of the hydroxychloroacetic acid resin, N,N-dimethylformamide F and toluene diisocyanate is: 1g: 30mL: 1.36mmol;

[0118] Its infrared data are as follows: 1740cm -1 :-C=O exists and is enhanced; 1276cm -1 :-CF exists; 3342cm -1 、1717cm -1: Carbamate exists and is enhanced; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO disappears; 733cm -1 :-C-Cl exists.

[0119] The functional modifier II is prepared by the following method:

[0120] Nano-SiO 2 Place in a reaction container filled with ethyl acetate A, after ultrasonic dispersion for 1 hour, add γ-(meth)acryloxypropyltrimethoxysilane and deionized water, slowly raise the temperature to 70°C, heat and stir for 10 hours; after the reaction is completed, cool to room temperature, filter, wash with ethyl acetate B, and vacuum dry at 80°C to constant weight to obtain the target product;

[0121] The nano-SiO 2 , ethyl acetate, γ-(meth)acryloxypropyltrimethoxysilane, deionized water, and ethyl acetate B are used in a ratio of 5.00 g: 200 mL: 35.00 g: 1.00 g: 600 mL;

[0122] Its infrared data is as follows: 3438cm -1 :-OH weakened; 1109cm -1 、801cm -1 :-Si-O- exists; 2928cm -1 :-CH exists; 1605cm -1 、810cm -1 :-C=C- exists.

[0123] A method for preparing an EB / excimer lamp-cured antifouling composition comprises the following steps:

[0124] Protect from light, keep humidity ≤60%, mix polyurethane acrylate resin, acrylate monomer, functional modifier I, functional modifier II, color paste, dispersant, defoamer and leveling agent according to the formula ratio, stir at a speed of 2000r / min for 30min, and obtain an EB / excimer lamp curing antifouling composition with a viscosity of 180cps.

[0125] A method for preparing an EB-cured antifouling coating comprises the following steps:

[0126] S1: The EB / excimer lamp curing antifouling composition is uniformly coated on the substrate, preheated at 60°C for 5 minutes, and placed under a 172nm excimer lamp for excimer lamp curing; the excimer lamp has an energy density of 2000mW / cm 2 , irradiation time 4s, oxygen content 150ppm.

[0127] S2: The coating obtained in S1 is subjected to EB curing to obtain an EB-cured anti-fouling coating with a thickness of 80±5 μm after drying; the EB curing has a radiation dose of 120 kGy and a radiation time of 4 s.

[0128] Example 2

[0129] An EB / excimer lamp curing antifouling composition comprises the following raw materials in parts by weight:

[0130] Polyurethane acrylate resin CN971A80 80 parts;

[0131] 10 parts of octadecyl acrylate;

[0132] 7 parts of diethylene glycol diacrylate;

[0133] 3 parts of propoxylated trimethylolpropane triacrylate;

[0134] Functional modifier I 15 parts;

[0135] Functional modifier II 5 parts;

[0136] Defoaming agent 0.1 part;

[0137] 0.2 parts of leveling agent.

[0138] The above functional modifier I is prepared by the following method:

[0139] (1) dissolving trimethylolpropane and triethylamine in N,N-dimethylformamide A in a reaction container, dissolving perfluorooctanoyl chloride in N,N-dimethylformamide B in a constant pressure dropping funnel, placing in an ice bath, stirring, and after the addition is completed, controlling the temperature to continue stirring at 0° C. for 14 hours, and after the reaction is completed; filtering, distilling under reduced pressure, dissolving the concentrate in dichloromethane A, adding saturated sodium bicarbonate solution to the solution, washing three times, and then washing with deionized water three times, separating the liquids, taking the organic phase, drying with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure, and drying under vacuum at 80° C. for 4 hours to obtain an intermediate product I;

[0140] The dosage ratio of trimethylolpropane, triethylamine, N,N-dimethylformamide A, perfluorooctanoyl chloride, N,N-dimethylformamide B, dichloromethane A, saturated sodium bicarbonate solution, deionized water, and anhydrous sodium sulfate is: 1 mol: 1.1 mol: 400 mL: 1.0 mol: 150 mL: 500 mL: 400 mL: 400 mL: 50 g;

[0141] Its infrared data is as follows: 3538cm -1 :-OH exists; 1737cm -1 :-C=O exists; 1276cm-1 :-CF exists.

[0142] (2) Dissolve the intermediate product I, dibutyltin dilaurate, and p-hydroxyanisole in N,N-dimethylformamide C and place them in a reaction container; dissolve isocyanoethyl methacrylate in N,N-dimethylformamide D and place them in a constant pressure dropping funnel; stir, dropwise add, and heat to 80° C.; continue stirring for 4 hours after the dropwise addition is completed, and let stand to obtain a mixed solution containing the intermediate product II;

[0143] The usage ratio of the intermediate product I, N,N-dimethylformamide C, isocyanoethyl methacrylate, and N,N-dimethylformamide D is: 1 mol: 300 mL: 1.1 mol: 200 mL;

[0144] The amount of dibutyltin dilaurate is 1wt% of the total mass of the reactants;

[0145] The dosage of the p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate;

[0146] Its infrared data is as follows: 3538cm -1 :-OH exists and weakens; 1737cm -1 :-C=O exists and is enhanced; 1276cm -1 :-CF exists; 3350cm -1 、1720cm -1 : Carbamate exists; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO does not exist.

[0147] (3) Dissolve isophorone diisocyanate in N,N-dimethylformamide E and place it in a reaction container. Place the mixed solution containing the intermediate product II in a constant pressure dropping funnel, stir, add dropwise, and heat to 90° C. After the addition is completed, continue stirring for 4 hours and let stand to obtain a solution containing the intermediate product III;

[0148] The ratio of the amount of isophorone diisocyanate, N,N-dimethylformamide E and the amount of the intermediate product I is: 1.1 mol: 300 mL: 1 mol;

[0149] Its infrared data is as follows: 3538cm -1 :-OH disappears; 1737cm -1 :-C=O exists; 1276cm -1 :-CF exists; 3350cm -1 、1720cm -1 : Carbamate exists and is enhanced; 1607cm-1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO exists.

[0150] (4) Dissolve the hydroxychloroacetic acid resin in N,N-dimethylformamide F, add it to the solution containing the intermediate product III, stir at 100° C. for 10 h, and after the reaction is completed, cool to room temperature, distill under reduced pressure, add methanol, take the precipitate, and dry it in vacuum at 40° C. for 24 h to obtain the target product IV;

[0151] The dosage ratio of the hydroxychloroacetic acid resin, N,N-dimethylformamide F and isophorone diisocyanate is: 1g: 30mL: 1.36mmol;

[0152] Its infrared data are as follows: 1740cm -1 :-C=O exists and is enhanced; 1276cm -1 :-CF exists; 3342cm -1 、1717cm -1 : Carbamate exists and is enhanced; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO disappears; 733cm -1 :-C-Cl exists.

[0153] The functional modifier II is prepared by the following method:

[0154] Nano-SiO 2 Place in a reaction container filled with ethyl acetate A, after ultrasonic dispersion for 1 hour, add γ-(meth)acryloxypropyltriethoxysilane and deionized water, slowly heat to 60°C, heat and stir for 14 hours; after the reaction, cool to room temperature, filter, wash with ethyl acetate B, and vacuum dry at 80°C to constant weight to obtain the target product;

[0155] The nano-SiO 2 , ethyl acetate, γ-(meth)acryloxypropyltriethoxysilane, deionized water, and ethyl acetate B are used in a ratio of 5.00 g: 200 mL: 35.00 g: 1.00 g: 600 mL;

[0156] Its infrared data is as follows: 3438cm -1 :-OH weakened; 1109cm -1 、801cm -1 :-Si-O- exists; 2928cm -1 :-CH exists; 1607cm -1 、811cm-1 :-C=C- exists.

[0157] The preparation method of an EB / excimer lamp curable antifouling composition is the same as that of the specific embodiment 1, except that the viscosity is 100 cps.

[0158] A method for preparing an EB-cured antifouling coating comprises the following steps:

[0159] S1: The EB / excimer lamp curing antifouling composition is uniformly coated on the substrate, preheated at 60°C for 5 minutes, and placed under a 172nm excimer lamp for excimer lamp curing; the excimer lamp energy density is 3000mW / cm 2 , irradiation time 3s, oxygen content 200ppm.

[0160] S2: The coating obtained in S1 is subjected to EB curing to obtain an EB-cured anti-fouling coating with a thickness of 80±5 μm after drying; the EB curing has a radiation dose of 160 kGy and a radiation time of 2 s.

[0161] Example 3

[0162] An EB / excimer lamp curing antifouling composition comprises the following raw materials in parts by weight:

[0163] Polyurethane acrylate resin CN970A60NS 75 parts;

[0164] 4 parts of isobornyl acrylate;

[0165] 4 parts of dipropylene glycol diacrylate;

[0166] 2 parts of ethoxylated pentaerythritol tripropylene glycol ester;

[0167] Functional modifier I 13 parts;

[0168] Functional modifier II 7 parts;

[0169] Defoaming agent 0.1 part;

[0170] 0.2 parts of leveling agent.

[0171] The above functional modifier I is prepared by the following method:

[0172] (1) dissolving trimethylolpropane and triethylamine in N,N-dimethylformamide A in a reaction container, dissolving perfluorooctanoyl chloride in N,N-dimethylformamide B in a constant pressure dropping funnel, placing in an ice bath, stirring, and after the addition is completed, stirring is continued at 5° C. for 8 hours. After the reaction is completed, filtering, distilling under reduced pressure, dissolving the concentrate in dichloromethane A, adding saturated sodium bicarbonate solution to the solution, washing 3 times, and then washing with deionized water 3 times, separating the liquids, taking the organic phase, drying with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure, and drying under vacuum at 80° C. for 4 hours to obtain intermediate product I;

[0173] The dosage ratio of trimethylolpropane, triethylamine, N,N-dimethylformamide A, perfluorooctanoyl chloride, N,N-dimethylformamide B, dichloromethane A, saturated sodium bicarbonate solution, deionized water, and anhydrous sodium sulfate is: 1 mol: 1.1 mol: 400 mL: 1.1 mol: 150 mL: 500 mL: 400 mL: 400 mL: 50 g;

[0174] Its infrared data is as follows: 3538cm -1 :-OH exists; 1737cm -1 :-C=O exists; 1276cm -1 :-CF exists.

[0175] (2) Dissolve the intermediate product I, dibutyltin dilaurate, and p-hydroxyanisole in N,N-dimethylformamide C and place them in a reaction container; dissolve isocyanoethyl methacrylate in N,N-dimethylformamide D and place them in a constant pressure dropping funnel; stir, dropwise add, and heat to 85° C.; continue stirring for 3 h after the dropwise addition is completed, and let stand to obtain a mixed solution containing the intermediate product II;

[0176] The usage ratio of the intermediate product I, N,N-dimethylformamide C, isocyanoethyl methacrylate, and N,N-dimethylformamide D is: 1 mol: 300 mL: 1.1 mol: 200 mL;

[0177] The amount of dibutyltin dilaurate is 1wt% of the total mass of the reactants;

[0178] The dosage of the p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate;

[0179] Its infrared data is as follows: 3538cm -1 :-OH exists and weakens; 1737cm -1 :-C=O exists and is enhanced; 1276cm -1 :-CF exists; 3350cm -1 、1720cm -1 : Carbamate exists; 1607cm -1、811cm -1 :-C=C- exists; 2275cm -1 :-NCO does not exist.

[0180] (3) Dissolve toluene diisocyanate in N,N-dimethylformamide E and place it in a reaction container. Place the mixed solution containing the intermediate product II in a constant pressure dropping funnel, stir, add dropwise, and heat to 70° C. After the addition is completed, continue stirring for 2 hours and let stand to obtain a solution containing the intermediate product III;

[0181] The ratio of the amount of toluene diisocyanate, N,N-dimethylformamide E to the amount of the intermediate product I is: 1.1 mol: 300 mL: 1 mol;

[0182] Its infrared data is as follows: 3538cm -1 :-OH disappears; 1737cm -1 :-C=O exists; 1276cm -1 :-CF exists; 3350cm -1 、1720cm -1 : Carbamate exists and is enhanced; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO exists.

[0183] (4) Dissolve the hydroxychloroacetate resin in N,N-dimethylformamide F, add the solution to the intermediate product III, stir at 90°C for 5 hours, cool to room temperature after the reaction, distill under reduced pressure, add methanol, take the precipitate, and dry it in vacuum at 40°C for 24 hours to obtain the target product IV;

[0184] The dosage ratio of the hydroxychloroacetic acid resin, N,N-dimethylformamide F and toluene diisocyanate is: 1g: 30mL: 1.36mmol;

[0185] Its infrared data are as follows: 1740cm -1 :-C=O exists and is enhanced; 1276cm -1 :-CF exists; 3342cm -1 、1717cm -1 : Carbamate exists and is enhanced; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO disappears; 733cm -1 :-C-Cl exists.

[0186] The functional modifier II is prepared by the following method:

[0187] Nano-SiO 2 Place in a reaction container filled with ethyl acetate A, ultrasonically disperse for 1 hour, add vinyl triethoxysilane and deionized water, slowly heat to 80°C, heat and stir for 6 hours; after the reaction, cool to room temperature, filter, wash with ethyl acetate B, and vacuum dry at 80°C to constant weight to obtain the target product;

[0188] The nano-SiO 2 , ethyl acetate, vinyl triethoxysilane, deionized water, and ethyl acetate B are used in a ratio of 5.00 g: 200 mL: 35.00 g: 1.00 g: 600 mL;

[0189] Its infrared data is as follows: 3438cm -1 :-OH weakened; 1109cm -1 、801cm -1 :-Si-O- exists; 2928cm -1 :-CH exists; 1621cm -1 :-C=C- exists.

[0190] The preparation method of an EB / excimer lamp curable antifouling composition is the same as that of Example 1, except that the viscosity is 220 cps.

[0191] A method for preparing an EB-cured antifouling coating comprises the following steps:

[0192] S1: The EB / excimer lamp curing antifouling composition is uniformly coated on the substrate, preheated at 60°C for 5 minutes, and placed under a 172nm excimer lamp for excimer lamp curing; the excimer lamp has an energy density of 2000mW / cm 2 , irradiation time 4s, oxygen content 150ppm.

[0193] S2: The coating obtained in S1 is subjected to EB curing to obtain an EB-cured anti-fouling coating with a thickness of 80±5 μm after drying; the EB curing has a radiation dose of 120 kGy and a radiation time of 5 s.

[0194] Example 4

[0195] An EB / excimer lamp curing antifouling composition comprises the following raw materials in parts by weight:

[0196] Polyurethane acrylate resin CN8009NS 80 parts;

[0197] 6 parts of 2-methoxyethyl acrylate;

[0198] Neopentyl glycol diacrylate 6 parts;

[0199] 3 parts of pentaerythritol tetraacrylate;

[0200] Functional modifier I 10 parts;

[0201] Functional modifier II 10 parts;

[0202] Defoaming agent 0.1 part;

[0203] 0.2 parts of leveling agent.

[0204] The above functional modifier I is prepared by the following method:

[0205] (1) dissolving trimethylolpropane and triethylamine in N,N-dimethylformamide A and placing them in a reaction container, dissolving perfluorooctanoyl chloride in N,N-dimethylformamide B and placing them in a constant pressure dropping funnel, placing them in an ice bath, stirring, and after the addition is completed, controlling the temperature to continue stirring at 0° C. for 12 hours. After the reaction is completed, filtering, distilling under reduced pressure, dissolving the concentrate in dichloromethane A, adding saturated sodium bicarbonate solution to the solution, washing it 3 times, and then washing it with deionized water 3 times, separating the liquids, taking the organic phase, drying it with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure, and drying it in a vacuum at 80° C. for 4 hours to obtain an intermediate product I;

[0206] The dosage ratio of trimethylolpropane, triethylamine, N,N-dimethylformamide A, perfluorooctanoyl chloride, N,N-dimethylformamide B, dichloromethane A, saturated sodium bicarbonate solution, deionized water, and anhydrous sodium sulfate is: 1 mol: 1.1 mol: 400 mL: 1.1 mol: 150 mL: 500 mL: 400 mL: 400 mL: 50 g;

[0207] Its infrared data is as follows: 3538cm -1 :-OH exists; 1737cm -1 :-C=O exists; 1276cm -1 :-CF exists.

[0208] (2) Dissolve the intermediate product I, dibutyltin dilaurate, and p-hydroxyanisole in N,N-dimethylformamide C and place them in a reaction container; dissolve isocyanoethyl methacrylate in N,N-dimethylformamide D and place them in a constant pressure dropping funnel; stir, dropwise add, and heat to 90° C.; continue stirring for 2 h after the dropwise addition is completed, and let stand to obtain a mixed solution containing the intermediate product II;

[0209] The usage ratio of the intermediate product I, N,N-dimethylformamide C, isocyanoethyl methacrylate, and N,N-dimethylformamide D is: 1 mol: 300 mL: 1.1 mol: 200 mL;

[0210] The amount of dibutyltin dilaurate is 1wt% of the total mass of the reactants;

[0211] The dosage of the p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate;

[0212] Its infrared data is as follows: 3538cm -1 :-OH exists and weakens; 1737cm -1 :-C=O exists and is enhanced; 1276cm -1 :-CF exists; 3350cm -1 、1720cm -1 : Carbamate exists; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO does not exist.

[0213] (3) Dissolve isophorone diisocyanate in N,N-dimethylformamide E and place it in a reaction container. Place the mixed solution containing the intermediate product II in a constant pressure dropping funnel, stir, add dropwise, and heat to 80° C. After the addition is completed, continue stirring for 4 hours and let stand to obtain a solution containing the intermediate product III;

[0214] The ratio of the amount of isophorone diisocyanate, N,N-dimethylformamide E and the amount of the intermediate product I is: 1.1 mol: 300 mL: 1 mol;

[0215] Its infrared data is as follows: 3538cm -1 :-OH disappears; 1737cm -1 :-C=O exists; 1276cm -1 :-CF exists; 3350cm -1 、1720cm -1 : Carbamate exists and is enhanced; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO exists.

[0216] (4) Dissolve the hydroxychloroacetic acid resin in N,N-dimethylformamide F, add it to the solution containing the intermediate product III, stir at 100° C. for 10 h, and after the reaction is completed, cool to room temperature, distill under reduced pressure, add methanol, take the precipitate, and dry it in vacuum at 40° C. for 24 h to obtain the target product IV;

[0217] The dosage ratio of the hydroxychloroacetic acid resin, N,N-dimethylformamide F and isophorone diisocyanate is: 1g: 30mL: 1.36mmol;

[0218] Its infrared data are as follows: 1740cm -1 :-C=O exists and is enhanced; 1276cm-1 :-CF exists; 3342cm -1 、1717cm -1 : Carbamate exists and is enhanced; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO disappears; 733cm -1 :-C-Cl exists.

[0219] The functional modifier II is prepared by the following method:

[0220] Nano-SiO 2 Place in a reaction container filled with ethyl acetate A, ultrasonically disperse for 1 hour, add vinyl tri(β-methoxyethoxy)silane and deionized water, slowly heat to 60°C, heat and stir for 12 hours; after the reaction, cool to room temperature, filter, wash with ethyl acetate B, and vacuum dry at 80°C to constant weight to obtain the target product;

[0221] The nano-SiO 2 , ethyl acetate, vinyl tri(β-methoxyethoxy)silane, deionized water, and ethyl acetate B are used in a ratio of 5.00 g: 200 mL: 35.00 g: 1.00 g: 600 mL;

[0222] Its infrared data is as follows: 3438cm -1 :-OH weakened; 1109cm -1 、801cm -1 :-Si-O- exists; 2928cm -1 :-CH exists; 1620cm -1 :-C=C- exists.

[0223] The preparation method of an EB / excimer lamp curable antifouling composition is the same as that of Example 1, except that the viscosity is 150 cps.

[0224] A method for preparing an EB-cured antifouling coating comprises the following steps:

[0225] S1: The EB / excimer lamp curing antifouling composition is uniformly coated on the substrate, preheated at 60°C for 5 minutes, and placed under a 172nm excimer lamp for excimer lamp curing; the excimer lamp has an energy density of 1500mW / cm 2 , irradiation time 5s, oxygen content 150ppm.

[0226] S2: The coating obtained in S1 is subjected to EB curing to obtain an EB-cured anti-fouling coating with a thickness of 80±5 μm after drying; the EB curing has a radiation dose of 120 kGy and a radiation time of 5 s.

[0227] Example 5

[0228] An EB / excimer lamp curing antifouling composition comprises the following raw materials in parts by weight:

[0229] Polyurethane acrylate resin CN9010NS 70 parts;

[0230] 5 parts of ethoxyethoxyethyl acrylate;

[0231] 5 parts of propoxy neopentyl glycol diacrylate;

[0232] Functional modifier I 10 parts;

[0233] Functional modifier II 8 parts;

[0234] Defoaming agent 0.1 part;

[0235] 0.2 parts of leveling agent.

[0236] The above functional modifier I is prepared by the following method:

[0237] (1) dissolving trimethylolpropane and triethylamine in N,N-dimethylformamide A and placing them in a reaction container, dissolving perfluorooctanoyl chloride in N,N-dimethylformamide B and placing them in a constant pressure dropping funnel, placing them in an ice bath, stirring, and after the addition is completed, controlling the temperature to continue stirring at 0° C. for 10 hours. After the reaction is completed, filtering, distilling under reduced pressure, dissolving the concentrate in dichloromethane A, adding saturated sodium bicarbonate solution to the solution, washing it 3 times, and then washing it with deionized water 3 times, separating the liquids, taking the organic phase, drying it with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure, and drying it in a vacuum at 80° C. for 4 hours to obtain an intermediate product I;

[0238] The dosage ratio of trimethylolpropane, triethylamine, N,N-dimethylformamide A, perfluorooctanoyl chloride, N,N-dimethylformamide B, dichloromethane A, saturated sodium bicarbonate solution, deionized water, and anhydrous sodium sulfate is: 1 mol: 1.1 mol: 400 mL: 1.1 mol: 150 mL: 500 mL: 400 mL: 400 mL: 50 g;

[0239] Its infrared data is as follows: 3538cm -1 :-OH exists; 1737cm -1 :-C=O exists; 1276cm -1 :-CF exists.

[0240] (2) Dissolve the intermediate product I, dibutyltin dilaurate, and p-hydroxyanisole in N,N-dimethylformamide C and place them in a reaction container; dissolve isocyanoethyl methacrylate in N,N-dimethylformamide D and place them in a constant pressure dropping funnel; stir, dropwise add, and heat to 80° C.; continue stirring for 3 h after the dropwise addition is completed, and let stand to obtain a mixed solution containing the intermediate product II;

[0241] The usage ratio of the intermediate product I, N,N-dimethylformamide C, isocyanoethyl methacrylate, and N,N-dimethylformamide D is: 1 mol: 300 mL: 1.1 mol: 200 mL;

[0242] The amount of dibutyltin dilaurate is 1wt% of the total mass of the reactants;

[0243] The dosage of the p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate;

[0244] Its infrared data is as follows: 3538cm -1 :-OH exists and weakens; 1737cm -1 :-C=O exists and is enhanced; 1276cm -1 :-CF exists; 3350cm -1 、1720cm -1 : Carbamate exists; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO does not exist.

[0245] (3) Dissolve toluene diisocyanate in N,N-dimethylformamide E and place it in a reaction container. Place the mixed solution containing the intermediate product II in a constant pressure dropping funnel, stir, add dropwise, and heat to 80° C. After the addition is completed, continue stirring for 2 hours and let stand to obtain a solution containing the intermediate product III;

[0246] The ratio of the amount of toluene diisocyanate, N,N-dimethylformamide E to the amount of the intermediate product I is: 1.1 mol: 300 mL: 1 mol;

[0247] Its infrared data is as follows: 3538cm -1 :-OH disappears; 1737cm -1 :-C=O exists; 1276cm -1 :-CF exists; 3350cm -1 、1720cm -1 : Carbamate exists and is enhanced; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm-1 :-NCO exists.

[0248] (4) Dissolve the hydroxychloroacetate resin in N,N-dimethylformamide F, add the solution to the intermediate product III, stir at 90°C for 5 hours, cool to room temperature after the reaction, distill under reduced pressure, add methanol, take the precipitate, and dry it in vacuum at 40°C for 24 hours to obtain the target product IV;

[0249] The dosage ratio of the hydroxychloroacetic acid resin, N,N-dimethylformamide F and toluene diisocyanate is: 1g: 30mL: 1.36mmol;

[0250] Its infrared data are as follows: 1740cm -1 :-C=O exists and is enhanced; 1276cm -1 :-CF exists; 3342cm -1 、1717cm -1 : Carbamate exists and is enhanced; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO disappears; 733cm -1 :-C-Cl exists.

[0251] The functional modifier II is prepared by the following method:

[0252] Nano-SiO 2 Place in a reaction container filled with ethyl acetate A, ultrasonically disperse for 1 hour, add 3-mercaptopropyltriethoxysilane and deionized water, slowly heat to 80°C, heat and stir for 8 hours; after the reaction, cool to room temperature, filter, wash with ethyl acetate B, and vacuum dry at 80°C to constant weight to obtain the target product;

[0253] The nano-SiO 2 , ethyl acetate, 3-mercaptopropyltriethoxysilane, deionized water, and ethyl acetate B in a dosage ratio of 5.00 g: 200 mL: 35.00 g: 1.00 g: 600 mL;

[0254] Its infrared data is as follows: 3438cm -1 :-OH weakened; 1109cm -1 、801cm -1 :-Si-O- exists; 2928cm -1 :-CH exists; 2550cm -1 :-SH exists.

[0255] The preparation method of an EB / excimer lamp curable antifouling composition is the same as that of the specific embodiment 1, except that the viscosity is 300 cps.

[0256] A method for preparing an EB-cured antifouling coating comprises the following steps:

[0257] S1: The EB / excimer lamp curing antifouling composition is uniformly coated on the substrate, preheated at 60°C for 5 minutes, and placed under a 172nm excimer lamp for excimer lamp curing; the excimer lamp energy density is 1000mW / cm 2 , irradiation time 5s, oxygen content 100ppm.

[0258] S2: The coating obtained in S1 is subjected to EB curing to obtain an EB-cured antifouling coating with a dry film thickness of 80±5 μm; the EB curing has a radiation dose of 100 kGy and a radiation time of 5 s.

[0259] Example 6

[0260] An EB / excimer lamp curing antifouling composition comprises the following raw materials in parts by weight:

[0261] Polyurethane acrylate resin CN9006NS 70 parts;

[0262] Ethoxylated neopentyl glycol methoxy monoacrylate 12 parts;

[0263] 8 parts of propoxy neopentyl glycol diacrylate;

[0264] Functional modifier I 12 parts;

[0265] Functional modifier II 6 parts;

[0266] Defoaming agent 0.1 part;

[0267] 0.2 parts of leveling agent.

[0268] The above functional modifier I is prepared by the following method:

[0269] (1) dissolving trimethylolpropane and triethylamine in N,N-dimethylformamide A in a reaction container, dissolving perfluorooctanoyl chloride in N,N-dimethylformamide B in a constant pressure dropping funnel, placing in an ice bath, stirring, and after the addition is completed, stirring is continued at 5° C. for 10 hours. After the reaction is completed, filtering, distilling under reduced pressure, dissolving the concentrate in dichloromethane A, adding saturated sodium bicarbonate solution to the solution, washing three times, and then washing with deionized water three times, separating the liquids, taking the organic phase, drying with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure, and drying under vacuum at 80° C. for 4 hours to obtain intermediate product I;

[0270] The dosage ratio of trimethylolpropane, triethylamine, N,N-dimethylformamide A, perfluorooctanoyl chloride, N,N-dimethylformamide B, dichloromethane A, saturated sodium bicarbonate solution, deionized water, and anhydrous sodium sulfate is: 1 mol: 1.1 mol: 400 mL: 1.1 mol: 150 mL: 500 mL: 400 mL: 400 mL: 50 g;

[0271] Its infrared data is as follows: 3538cm -1 :-OH exists; 1737cm -1 :-C=O exists; 1276cm -1 :-CF exists.

[0272] (2) Dissolve the intermediate product I, dibutyltin dilaurate, and p-hydroxyanisole in N,N-dimethylformamide C and place them in a reaction container; dissolve isocyanoethyl methacrylate in N,N-dimethylformamide D and place them in a constant pressure dropping funnel; stir, dropwise add, and heat to 90° C.; continue stirring for 4 h after the dropwise addition is completed, and let stand to obtain a mixed solution containing the intermediate product II;

[0273] The usage ratio of the intermediate product I, N,N-dimethylformamide C, isocyanoethyl methacrylate, and N,N-dimethylformamide D is: 1 mol: 300 mL: 1.1 mol: 200 mL;

[0274] The amount of dibutyltin dilaurate is 1wt% of the total mass of the reactants;

[0275] The dosage of the p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate;

[0276] Its infrared data is as follows: 3538cm -1 :-OH exists and weakens; 1737cm -1 :-C=O exists and is enhanced; 1276cm -1 :-CF exists; 3350cm -1 、1720cm -1 : Carbamate exists; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO does not exist.

[0277] (3) Dissolve toluene diisocyanate in N,N-dimethylformamide E and place it in a reaction container. Place the mixed solution containing the intermediate product II in a constant pressure dropping funnel, stir, add dropwise, and heat to 60° C. After the addition is completed, continue stirring for 2 hours and let stand to obtain a solution containing the intermediate product III;

[0278] The ratio of the amount of toluene diisocyanate, N,N-dimethylformamide E to the amount of the intermediate product I is: 1.1 mol: 300 mL: 1 mol;

[0279] Its infrared data is as follows: 3538cm -1 :-OH disappears; 1737cm -1 :-C=O exists; 1276cm -1 :-CF exists; 3350cm -1 、1720cm -1 : Carbamate exists and is enhanced; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO exists.

[0280] (4) Dissolve the hydroxychloroacetate resin in N,N-dimethylformamide F, add the solution to the intermediate product III, stir at 80°C for 8 hours, cool to room temperature after the reaction, distill under reduced pressure, add methanol, take the precipitate, and dry it in vacuum at 40°C for 24 hours to obtain the target product IV;

[0281] The dosage ratio of the hydroxychloroacetic acid resin, N,N-dimethylformamide F and toluene diisocyanate is: 1g: 30mL: 1.36mmol;

[0282] Its infrared data are as follows: 1740cm -1 :-C=O exists and is enhanced; 1276cm -1 :-CF exists; 3342cm -1 、1717cm -1 : Carbamate exists and is enhanced; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO disappears; 733cm -1 :-C-Cl exists.

[0283] The functional modifier II is prepared by the following method:

[0284] Nano-SiO 2 Place in a reaction container filled with ethyl acetate A, ultrasonically disperse for 1 hour, add 3-mercaptopropylmethyldimethoxysilane and deionized water, slowly heat to 70°C, heat and stir for 8 hours; after the reaction, cool to room temperature, filter, wash with ethyl acetate B, and vacuum dry at 80°C to constant weight to obtain the target product;

[0285] The nano-SiO 2, ethyl acetate, 3-mercaptopropylmethyldimethoxysilane, deionized water, and ethyl acetate B in a dosage ratio of 5.00 g: 200 mL: 35.00 g: 1.00 g: 600 mL;

[0286] Its infrared data is as follows: 3438cm -1 :-OH weakened; 1109cm -1 、801cm -1 :-Si-O- exists; 2928cm -1 :-CH exists; 2550cm -1 :-SH exists.

[0287] The preparation method of an EB / excimer lamp curable antifouling composition is the same as that of the specific embodiment 1, except that the viscosity is 200 cps.

[0288] A method for preparing an EB-cured antifouling coating comprises the following steps:

[0289] S1: The EB / excimer lamp curing antifouling composition is uniformly coated on the substrate, preheated at 60°C for 5 minutes, and placed under a 172nm excimer lamp for excimer lamp curing; the excimer lamp has an energy density of 1500mW / cm 2 , irradiation time 4s, oxygen content 150ppm.

[0290] S2: The coating obtained in S1 is subjected to EB curing to obtain an EB-cured anti-fouling coating with a thickness of 80±5 μm after drying; the EB curing has a radiation dose of 150 kGy and a radiation time of 3 s.

[0291] Example 7

[0292] An EB / excimer lamp curing antifouling composition comprises the following raw materials in parts by weight:

[0293] Polyurethane acrylate resin CN9110NS 70 parts;

[0294] 6 parts of octadecyl acrylate;

[0295] 4 parts of isobornyl acrylate;

[0296] Neopentyl glycol diacrylate 5 parts;

[0297] Functional modifier I 13 parts;

[0298] Functional modifier II 5 parts;

[0299] Defoaming agent 0.1 part;

[0300] 0.2 parts of leveling agent.

[0301] The preparation method of the functional modifier I is the same as that of specific embodiment 1.

[0302] The preparation method of the functional modifier II is the same as that of specific embodiment 1.

[0303] The preparation method of an EB / excimer lamp curable antifouling composition is the same as that of the specific embodiment 1, except that the viscosity is 250 cps.

[0304] A method for preparing an EB-cured antifouling coating comprises the following steps:

[0305] S1: The EB / excimer lamp curing antifouling composition is uniformly coated on the substrate, preheated at 60°C for 5 minutes, and placed under a 172nm excimer lamp for excimer lamp curing; the excimer lamp has an energy density of 2000mW / cm 2 , irradiation time 2s, oxygen content 120ppm.

[0306] S2: The coating obtained in S1 is subjected to EB curing to obtain an EB-cured antifouling coating with a thickness of 80±5 μm after drying; the EB curing has a radiation dose of 200 kGy and a radiation time of 2 s.

[0307] Example 8

[0308] An EB / excimer lamp curing antifouling composition comprises the following raw materials in parts by weight:

[0309] Polyurethane acrylate resin CN970A60NS 80 parts;

[0310] 6 parts of isooctyl acrylate;

[0311] 1. 6 parts of 6-hexanediol diacrylate;

[0312] 3 parts of ethoxylated trimethylolpropane triacrylate;

[0313] Functional modifier I 12 parts;

[0314] Functional modifier II 8 parts;

[0315] Color paste (organic medium yellow) 2.0 parts;

[0316] 0.5 parts of dispersant;

[0317] 0.5 parts of defoaming agent;

[0318] 0.5 parts of leveling agent.

[0319] The preparation method of the functional modifier I is the same as that of specific embodiment 1.

[0320] The preparation method of the functional modifier II is the same as that of specific embodiment 1.

[0321] The preparation method of an EB / excimer lamp-cured antifouling composition is the same as that of specific embodiment 1.

[0322] A method for preparing an EB-cured antifouling coating comprises the following steps:

[0323] S1: The EB / excimer lamp curing antifouling composition is uniformly coated on the substrate, preheated at 60°C for 5 minutes, and placed under a 172nm excimer lamp for excimer lamp curing; the excimer lamp energy density is 4000mW / cm 2 , irradiation time 10s, oxygen content 5ppm.

[0324] S2: The coating obtained in S1 is subjected to EB curing to obtain an EB-cured anti-fouling coating with a thickness of 80±5 μm after drying; the EB curing has a radiation dose of 150 kGy and a radiation time of 5 s.

[0325] Example 9

[0326] An EB / excimer lamp curing antifouling composition comprises the following raw materials in parts by weight:

[0327] Polyurethane acrylate resin CN970A60NS 80 parts;

[0328] 6 parts of isooctyl acrylate;

[0329] 1. 6 parts of 6-hexanediol diacrylate;

[0330] 3 parts of ethoxylated trimethylolpropane triacrylate;

[0331] Functional modifier I 12 parts;

[0332] Functional modifier II 8 parts;

[0333] Color paste (color blue) 3.0 parts;

[0334] Dispersant 0.2 parts;

[0335] 0.4 parts of defoaming agent;

[0336] 0.4 parts of leveling agent.

[0337] The preparation method of the functional modifier I is the same as that of specific embodiment 1.

[0338] The preparation method of the functional modifier II is the same as that of specific embodiment 1.

[0339] The preparation method of an EB / excimer lamp-cured antifouling composition is the same as that of specific embodiment 1.

[0340] A method for preparing an EB-cured antifouling coating comprises the following steps:

[0341] S1: The EB / excimer lamp curing antifouling composition is uniformly coated on the substrate, preheated at 60°C for 5 minutes, and placed under a 172nm excimer lamp for excimer lamp curing; the excimer lamp energy density is 4000mW / cm 2 , irradiation time 10s, oxygen content 5ppm.

[0342] S2: The coating obtained in S1 is subjected to EB curing to obtain an EB-cured anti-fouling coating with a thickness of 80±5 μm after drying; the EB curing has a radiation dose of 150 kGy and a radiation time of 5 s.

[0343] Example 10

[0344] An EB / excimer lamp curing antifouling composition comprises the following raw materials in parts by weight:

[0345] Polyurethane acrylate resin CN970A60NS 80 parts;

[0346] 6 parts of isooctyl acrylate;

[0347] 1. 6 parts of 6-hexanediol diacrylate;

[0348] 3 parts of ethoxylated trimethylolpropane triacrylate;

[0349] Functional modifier I 12 parts;

[0350] Functional modifier II 8 parts;

[0351] Color paste (UV extra white) 5.0 parts;

[0352] 0.4 parts of dispersant;

[0353] 0.2 parts of defoaming agent;

[0354] 0.3 parts of leveling agent.

[0355] The preparation method of the functional modifier I is the same as that of specific embodiment 1.

[0356] The preparation method of the functional modifier II is the same as that of specific embodiment 1.

[0357] The preparation method of an EB / excimer lamp-cured antifouling composition is the same as that of specific embodiment 1.

[0358] A method for preparing an EB-cured antifouling coating comprises the following steps:

[0359] S1: The EB / excimer lamp curing antifouling composition is uniformly coated on the substrate, preheated at 60°C for 5 minutes, and placed under a 172nm excimer lamp for excimer lamp curing; the excimer lamp energy density is 5000mW / cm 2, irradiation time 8s, oxygen content 50ppm.

[0360] S2: The coating obtained in S1 is subjected to EB curing to obtain an EB-cured anti-fouling coating with a thickness of 80±5 μm after drying; the EB curing has a radiation dose of 150 kGy and a radiation time of 5 s.

[0361] Comparative Examples 1-10 are compared with Example 1:

[0362] Comparative Example 1

[0363] An EB / excimer lamp-cured antifouling composition is the same as that in Specific Example 1, except that the functional modifier I and the functional modifier II are not added.

[0364] The preparation method of an EB / excimer lamp-cured antifouling composition is the same as that of specific embodiment 1.

[0365] A method for preparing an EB-cured antifouling coating is the same as that in specific embodiment 1.

[0366] Application Implementation Comparative Example 2

[0367] An EB / excimer lamp-cured antifouling composition is the same as that in Specific Example 1, except that the functional modifier I is not added.

[0368] The preparation method of an EB / excimer lamp-cured antifouling composition is the same as that of specific embodiment 1.

[0369] A method for preparing an EB-cured antifouling coating is the same as that in specific embodiment 1.

[0370] Application Implementation Comparative Example 3

[0371] An EB / excimer lamp curing antifouling composition is the same as that in Specific Example 1. The difference is that the preparation method of the functional modifier I is as follows:

[0372] Dissolve trimethylolpropane and triethylamine in N,N-dimethylformamide A and place them in a reaction container; dissolve perfluorooctanoyl chloride in N,N-dimethylformamide B and place them in a constant pressure dropping funnel, place in an ice bath, stir, and after the addition is completed, continue stirring at 5°C for 10 hours. After the reaction is completed; filter, distill under reduced pressure, dissolve the concentrate in dichloromethane A, add saturated sodium bicarbonate solution to the solution, wash 3 times, and then wash with deionized water 3 times, separate the liquids, take the organic phase, dry it with anhydrous sodium sulfate, filter, distill the filtrate under reduced pressure, and vacuum dry it at 80°C for 4 hours to obtain the target product;

[0373] The dosage ratio of trimethylolpropane, triethylamine, N,N-dimethylformamide A, perfluorooctanoyl chloride, N,N-dimethylformamide B, dichloromethane A, saturated sodium bicarbonate solution, deionized water, and anhydrous sodium sulfate is: 1 mol: 3.5 mol: 400 mL: 3.5 mol: 150 mL: 500 mL: 400 mL: 400 mL: 50 g;

[0374] Its infrared data is as follows: 3538cm -1 :-OH disappears; 1737cm -1 :-C=O exists; 1276cm -1 :-CF exists.

[0375] The preparation method of an EB / excimer lamp-cured antifouling composition is the same as that of specific embodiment 1.

[0376] A method for preparing an EB-cured antifouling coating is the same as that in specific embodiment 1.

[0377] Application Implementation Comparative Example 4

[0378] An EB / excimer lamp curing antifouling composition is the same as that in Specific Example 1. The difference is that the preparation method of the functional modifier I is as follows:

[0379] (1) dissolving trimethylolpropane and triethylamine in N,N-dimethylformamide A in a reaction container, dissolving perfluorooctanoyl chloride in N,N-dimethylformamide B in a constant pressure dropping funnel, placing in an ice bath, stirring, and after the addition is completed, stirring is continued at 5° C. for 10 hours. After the reaction is completed, filtering, distilling under reduced pressure, dissolving the concentrate in dichloromethane A, adding saturated sodium bicarbonate solution to the solution, washing three times, and then washing with deionized water three times, separating the liquids, taking the organic phase, drying with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure, and drying under vacuum at 80° C. for 4 hours to obtain intermediate product I;

[0380] The dosage ratio of trimethylolpropane, triethylamine, N,N-dimethylformamide A, perfluorooctanoyl chloride, N,N-dimethylformamide B, dichloromethane A, saturated sodium bicarbonate solution, deionized water, and anhydrous sodium sulfate is: 1 mol: 1.1 mol: 400 mL: 1.1 mol: 150 mL: 500 mL: 400 mL: 400 mL: 50 g;

[0381] Its infrared data is as follows: 3538cm -1 :-OH exists; 1737cm -1 :-C=O exists; 1276cm -1 :-CF exists.

[0382] (2) The intermediate product I, dibutyltin dilaurate, and p-hydroxyanisole are dissolved in N,N-dimethylformamide C and placed in a reaction container, and methylisocyanate is dissolved in N,N-dimethylformamide D and placed in a constant pressure dropping funnel, stirred, added dropwise, and heated to 90° C. After the addition is completed, stirring is continued for 3 h, allowed to stand, and vacuum distilled, and dried at 40° C. in a vacuum oven for 24 h to obtain the target product;

[0383] The usage ratio of the intermediate product I, N,N-dimethylformamide C, isocyanoethyl methacrylate, and N,N-dimethylformamide D is: 1 mol: 300 mL: 2.5 mol: 200 mL;

[0384] The amount of dibutyltin dilaurate is 1wt% of the total mass of the reactants;

[0385] The dosage of the p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate;

[0386] Its infrared data is as follows: 3538cm -1 :-OH disappears; 1737cm -1 :-C=O exists and is enhanced; 1276cm -1 :-CF exists; 3350cm -1 、1720cm -1 : Carbamate exists; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO does not exist.

[0387] The preparation method of an EB / excimer lamp-cured antifouling composition is the same as that of specific embodiment 1.

[0388] A method for preparing an EB-cured antifouling coating is the same as that in specific embodiment 1.

[0389] Application Implementation Comparative Example 5

[0390] An EB / excimer lamp curing antifouling composition is the same as that in Specific Example 1. The difference is that the preparation method of the functional modifier I is as follows:

[0391] (1) dissolving trimethylolpropane and triethylamine in N,N-dimethylformamide A in a reaction container, dissolving perfluorooctanoyl chloride in N,N-dimethylformamide B in a constant pressure dropping funnel, placing in an ice bath, stirring, and after the addition is completed, stirring is continued at 5° C. for 10 hours. After the reaction is completed, filtering, distilling under reduced pressure, dissolving the concentrate in dichloromethane A, adding saturated sodium bicarbonate solution to the solution, washing three times, and then washing with deionized water three times, separating the liquids, taking the organic phase, drying with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure, and drying under vacuum at 80° C. for 4 hours to obtain intermediate product I;

[0392] The dosage ratio of trimethylolpropane, triethylamine, N,N-dimethylformamide A, perfluorooctanoyl chloride, N,N-dimethylformamide B, dichloromethane A, saturated sodium bicarbonate solution, deionized water, and anhydrous sodium sulfate is: 1 mol: 1.1 mol: 400 mL: 1.1 mol: 150 mL: 500 mL: 400 mL: 400 mL: 50 g;

[0393] Its infrared data is as follows: 3538cm -1 :-OH exists; 1737cm -1 :-C=O exists; 1276cm -1 :-CF exists.

[0394] (2) Dissolve the intermediate product I, dibutyltin dilaurate, and p-hydroxyanisole in N,N-dimethylformamide C and place them in a reaction container; dissolve isocyanoethyl methacrylate in N,N-dimethylformamide D and place them in a constant pressure dropping funnel; stir, dropwise add, and heat to 90° C.; continue stirring for 3 h after the dropwise addition is completed, and let stand to obtain a mixed solution containing the intermediate product II;

[0395] The usage ratio of the intermediate product I, N,N-dimethylformamide C, isocyanoethyl methacrylate, and N,N-dimethylformamide D is: 1 mol: 300 mL: 1.1 mol: 200 mL;

[0396] The amount of dibutyltin dilaurate is 1wt% of the total mass of the reactants;

[0397] The dosage of the p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate;

[0398] Its infrared data is as follows: 3538cm -1 :-OH exists and weakens; 1737cm -1 :-C=O exists and is enhanced; 1276cm -1 :-CF exists; 3350cm -1 、1720cm -1 : Carbamate exists; 1607cm -1、811cm -1 :-C=C- exists; 2275cm -1 :-NCO does not exist.

[0399] (3) Add toluene diisocyanate to the mixed solution containing the intermediate product II in a constant pressure dropping funnel, stir, dropwise add, and heat to 60° C. After the dropwise addition is completed, continue stirring for 3 h, let stand, distill under reduced pressure, and vacuum dry at 40° C. for 24 h to obtain the target product;

[0400] The ratio of the amount of toluene diisocyanate to the amount of intermediate product I is: 1.0 mol: 2.2 mol;

[0401] Its infrared data is as follows: 3538cm -1 :-OH disappears; 1737cm -1 :-C=O exists; 1276cm -1 :-CF exists; 3350cm -1 、1720cm -1 : Carbamate exists and is enhanced; 1607cm -1 、811cm -1 :-C=C- exists; 2275cm -1 :-NCO does not exist.

[0402] The preparation method of an EB / excimer lamp-cured antifouling composition is the same as that of specific embodiment 1.

[0403] A method for preparing an EB-cured antifouling coating is the same as that in specific embodiment 1.

[0404] Application Implementation Comparative Example 6

[0405] An EB / excimer lamp curing antifouling composition is the same as that in Specific Example 1, except that no functional modifier II is added.

[0406] The preparation method of an EB / excimer lamp-cured antifouling composition is the same as that of specific embodiment 1.

[0407] A method for preparing an EB-cured antifouling coating is the same as that in specific embodiment 1.

[0408] Application Implementation Comparative Example 7

[0409] An EB / excimer lamp-cured antifouling composition is the same as that in Specific Example 1, except that the functional modifier II is replaced by nano-silicon dioxide.

[0410] The preparation method of an EB / excimer lamp-cured antifouling composition is the same as that of specific embodiment 1.

[0411] A method for preparing an EB-cured antifouling coating is the same as that in specific embodiment 1.

[0412] Application Implementation Comparative Example 8

[0413] An EB / excimer lamp curing antifouling composition is the same as that in specific embodiment 1.

[0414] The preparation method of an EB / excimer lamp-cured antifouling composition is the same as that of specific embodiment 1.

[0415] A method for preparing an EB-cured antifouling coating comprises the following steps:

[0416] The EB / excimer lamp curing antifouling composition was uniformly coated on the substrate, preheated at 60°C for 5 minutes, and placed under a 172nm excimer lamp for excimer lamp curing to obtain a coating with a thickness of 80±5μm after drying; the energy density of the excimer lamp was 2000mW / cm 2 , irradiation time 4s, oxygen content 150ppm.

[0417] Application Implementation Comparative Example 9

[0418] An EB / excimer lamp curing antifouling composition is the same as that in specific embodiment 1.

[0419] The preparation method of an EB / excimer lamp-cured antifouling composition is the same as that of specific embodiment 1.

[0420] A method for preparing an EB-cured antifouling coating comprises the following steps:

[0421] The EB / excimer lamp curing antifouling composition is uniformly coated on the substrate, preheated at 60°C for 5 minutes, and EB cured to obtain an EB cured antifouling coating with a thickness of 80±5 μm after dry film; the EB curing has a radiation dose of 120 kGy, a radiation time of 4 seconds, and an oxygen content of 150 ppm.

[0422] Application Implementation Comparative Example 10

[0423] An EB / excimer lamp curing antifouling composition is the same as that in specific embodiment 1.

[0424] The preparation method of an EB / excimer lamp-cured antifouling composition is the same as that of specific embodiment 1.

[0425] A method for preparing an EB-cured antifouling coating comprises the following steps:

[0426] S1: The EB / excimer lamp curing antifouling composition is uniformly coated on the substrate, preheated at 60°C for 5 minutes, and EB cured to obtain an EB cured antifouling coating with a thickness of 80±5 μm after the dry film; the EB curing has a radiation dose of 120 kGy and a radiation time of 4 seconds.

[0427] S2: The coating obtained in S1 is placed under a 172nm excimer lamp for excimer lamp curing; the energy density of the excimer lamp is 2000mW / cm 2 , irradiation time 4s, oxygen content 150ppm.

[0428] The physical properties of the EB / UV cured antifouling coatings prepared in Application Examples 1-10 and Application Comparative Examples 1-10 of the present invention were measured respectively, and the results are shown in Table 1.

[0429] Table 1 Physical test performance of each embodiment

[0430]

[0431]

[0432] It can be observed from Examples 1 to 10 that the EB / excimer lamp-cured antifouling composition of the present invention has properties such as matte, antifouling, anti-fingerprint, high hardness and scratch resistance.

[0433] From Example 1 and Comparative Examples 1-7, it can be observed that the self-made functional modifier I and functional modifier II of the present invention have positive effects on anti-fouling including anti-fingerprint, continuous anti-fouling and high hardness. From Example 1 and Comparative Example 3, it can be observed that the non-reactive fluorine-containing structure destroys the surface coating after friction, resulting in a sharp decrease in the water contact angle; from Example 1 and Comparative Examples 4-5, it can be observed that the high-functionality structure has advantages in mechanical properties and continuous anti-fouling; from Example 1 and Comparative Examples 1-2, 6-7, it can be observed that the compound use of functional modifiers I and II can play a better effect.

[0434] It can be observed from Example 1 and Comparative Examples 8-10 that the combination of EB curing and excimer lamp curing can obtain a product with high surface performance, high hardness, high scratch resistance, matte effect, etc., and the effect of first excimer lamp curing and then EB curing is better in terms of process.

[0435] The test method is as follows:

[0436] (1) Appearance: Check the surface for wrinkles and smoothness. It is better if the colored coating has no floating color. If the coating has wrinkles, feels smooth and has no floating color, it is recorded as "OK". Otherwise, it is recorded as "NG".

[0437] (2) Gloss: Tested using a gloss meter.

[0438] (3) Pencil hardness: tested in accordance with GB / T 6739-2022.

[0439] (4) Adhesion: Adhesion test was performed according to the method described in ASTM D3359-17.

[0440] (5) Water contact angle: measured in accordance with GB / T 30693-2014. The water contact angle was tested before and after friction, wherein the friction test conditions were 750 g weight and 0000# steel wool rubbed 100 times.

[0441] (6) Scratch resistance: tested according to the method described in ASTM D5178-2001.

[0442] Based on the above ideal embodiments of the present invention, the relevant staff can make various changes and modifications without departing from the technical concept of the present invention through the above description. The technical scope of the present invention is not limited to the contents of the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. An EB / excimer lamp curing antifouling composition, characterized in that: The invention comprises the following raw materials in parts by weight: Polyurethane acrylate resin 70-80 parts; Acrylate monomer 10-20 parts; Function modifier I 10-15 parts; Functional modifier II 5-10 parts; Color paste 0-5.0 parts; Dispersant 0-0.5 parts; Defoaming agent 0.1-0.5 parts; Leveling agent 0.2-0.5 parts; Wherein, the preparation method of the functional modifier I comprises the following steps: (1) esterifying trimethylolpropane and perfluorooctanoyl chloride in the presence of an acid-binding agent, triethylamine, to obtain an intermediate product I; (2) allowing the intermediate product I and isocyanoethyl methacrylate to undergo a nucleophilic addition reaction in the presence of a polymerization inhibitor, p-hydroxyanisole, and a catalyst, dibutyltin dilaurate, to obtain a mixed solution containing the intermediate product II; (3) adding an asymmetric diisocyanate to the mixed solution containing the intermediate product II to carry out an affinity addition reaction to obtain a solution containing the intermediate product III; (4) adding hydroxychloroacetic acid resin to the solution containing the intermediate product III to undergo affinity addition reaction to obtain the target product IV, i.e., the functional modifier I; The preparation method of the functional modifier II is as follows: Conducting coupling reaction between nano-SiO2 and silane coupling agent to obtain target product, i.e. functional modifier II; The silane coupling agent is a silane coupling agent containing a carbon-carbon double bond or a silane coupling agent containing a mercapto group; the dosage ratio of the nano-SiO2, the silane coupling agent and the deionized water is: 5.00g: 35.00g: 1.00g.

2. The EB / excimer lamp curing antifouling composition according to claim 1, characterized in that: The usage ratio of trimethylolpropane, triethylamine and perfluorooctanoyl chloride is 1 mol: 1.0-1.1mol:1.0-1.1mol; The ratio of the intermediate product I to isocyanoethyl methacrylate is 1 mol:1.1 mol; The dosage of the polymerization inhibitor p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate; The amount of the catalyst dibutyltin dilaurate used is 1wt% of the total mass of the reactants.

3. The EB / excimer lamp curing antifouling composition according to claim 1, characterized in that: The asymmetric diisocyanate is toluene diisocyanate or isophorone diisocyanate; the usage ratio of the asymmetric diisocyanate to the intermediate product I is 1.1 mol:1 mol; the usage ratio of the hydroxychloroacetic acid resin to the asymmetric diisocyanate is 1 g:1.36 mmol.

4. A method for preparing an EB / excimer lamp curable antifouling composition according to any one of claims 1 to 3, characterized in that: The steps include: Protect from light, keep humidity ≤60%, mix polyurethane acrylate resin, acrylate monomer, functional modifier I, functional modifier II, color paste, dispersant, defoamer and leveling agent according to the formula ratio, stir at a speed of 2000r / min for 30min, and obtain an EB / excimer lamp curing antifouling composition.

5. A method for preparing an EB-cured antifouling coating, characterized in that: The steps include: S1: uniformly coating the EB / excimer lamp-cured antifouling composition as described in any one of claims 1 to 3 on a substrate, preheating at 60° C. for 5 min, and placing under a 172 nm excimer lamp for excimer lamp curing; S2: The coating obtained in S1 is subjected to EB curing to obtain an EB-cured anti-fouling coating.

6. The method for preparing an EB-cured antifouling coating according to claim 5, characterized in that: The energy density of the excimer lamp is 1000-5000 mW / cm 2 , irradiation time 2-10s, oxygen content 5-200ppm; the EB curing has a radiation dose of 100-200kGy and a irradiation time of 2-5s.

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