CN112812685B - A kind of light-curing anti-graffiti coating with self-healing function and preparation method and application thereof - Google Patents

Abstract

The invention discloses a light-curing anti-graffiti coating with self-healing function and a preparation method and application thereof. The components are by weight: 10-70 parts of UV-curable polyurethane resin, 10-40 parts of reactive diluent, 5-30 parts of modified nanoparticles, and 0.5-10 parts of photoinitiator , 0.1 to 10 parts of additives. The coating formed by the coating of the present invention has good surface uniformity and smoothness, low surface energy, and it is difficult for graffiti substances and dirt to penetrate into the coating film; at the same time, after the coating surface is physically worn, the hydrophobic substances in the coating It migrates to the surface in hot and humid conditions and repairs the damaged surface by itself, restoring its anti-graffiti properties, thus ensuring the durability of the coating for outdoor use.

Description

A kind of light-curing anti-graffiti coating with self-healing function and preparation method and application thereof

technical field

The invention belongs to an anti-graffiti paint, and in particular relates to a light-curing anti-graffiti paint with self-healing function and a preparation method and application thereof.

Background technique

In recent years, the phenomenon of graffiti scribbled in urban buildings and public facilities has become increasingly serious, which not only seriously affects the image of a city, but also brings great trouble to advertising operations. Therefore, the coatings industry is faced with a huge challenge, which is the need to develop coatings with anti-graffiti properties. Anti-graffiti paint is a kind of paint with special surface function, the surface has low surface tension, the dirt rolls off naturally, and it will fall off easily after the sticker is attached. Designed to remove graffiti with an easy clean-up method, using only water if possible. However, the anti-graffiti coatings currently have the following problems: (1) the surface efficacy is easy to lose; (2) the coating process is complicated; (3) it is not easy to apply on a large scale. Therefore, it is of great significance to develop UV-curable anti-graffiti coating materials with self-healing function.

At present, there is no report on the preparation method of self-healing anti-graffiti coatings, but researchers have done some work on long-term anti-graffiti coatings. Patent CN104946110A proposes a preparation method of anti-graffiti, anti-fouling and anti-sticking high-weather-resistant paint, the method uses modified hydroxy acrylic resin, fluorocarbon resin, polyorganosiloxane, organosilicon modified acrylate and curing agent as raw materials The anti-graffiti coating is prepared, which not only has good anti-graffiti property, but also has good scrub resistance, solvent resistance and weather resistance. Patent CN102876150A reports that high weather resistance, anti-sticking and anti-graffiti water-based paint is prepared by using hydroxyl-containing fluorocarbon emulsion, anti-graffiti resin, hydrophilic isocyanate curing agent and water as the main raw materials. Although the anti-graffiti properties and weather resistance of the coatings prepared by the above methods have been significantly improved, the surface anti-graffiti properties of these coatings will decrease after many external physical abrasions, and they have no self-healing function, which will Affect the long-term service of the coating.

SUMMARY OF THE INVENTION

Purpose of the invention: In view of the problems existing in the prior art, the present invention provides a light-curing anti-graffiti coating with self-healing function. Low, it is difficult for graffiti substances and dirt to penetrate into the coating film; at the same time, after the coating surface is physically worn, the fluorosilane grafted on the nanoparticles in the coating will migrate to the surface under humid and hot conditions to repair the damaged surface by itself , its anti-graffiti properties are restored, thus ensuring the durability of the coating for outdoor use.

The invention also provides the preparation method and application of the photocurable anti-graffiti paint with self-healing function.

Technical solution: In order to solve the above problems, the light-curing anti-graffiti coating with self-healing function described in the present invention is mainly composed of UV-curable polyurethane resin, reactive diluent, hydrophobically modified nanoparticles, photoinitiator and auxiliary materials. The components are by weight: 10-70 parts of UV-curable polyurethane resin, 10-40 parts of reactive diluent, 5-30 parts of modified nanoparticles, and 0.5-10 parts of photoinitiator , 0.1 to 10 parts of additives.

Wherein, the UV-curable polyurethane resin is composed of one or more of isophorone diisocyanate or hexamethylene diisocyanate, one or more of polyethylene glycol or polypropylene glycol or polycarbonate glycol. Several and hydroxyl-terminated fluorine-containing silicone oils are dissolved in an organic solvent to obtain a uniform mixed solution and a catalyst is added. After stirring the reaction, the methacrylate-β-hydroxyethyl ester or pentaerythritol triacrylate or dipentaerythritol pentaacrylate is added. One or more, the polymerization inhibitor hydroquinone and the organic solvent are mixed uniformly and then added to the mixture, and the reaction is continued to be stirred to obtain the ultraviolet-curable polyurethane resin.

Preferably, the UV-curable polyurethane resin is composed of 0.2-6 parts by mass of one or more of isophorone diisocyanate or hexamethylene diisocyanate, and 0.2-20 parts by mass of polyethylene glycol or polyethylene glycol. One or more of propylene glycol or polycarbonate diol and 0.2-12 parts by mass of hydroxyl-terminated fluorine-containing silicone oil are dissolved in 2-20 parts by mass of an organic solvent to obtain a uniform mixed solution, and 0.1-1 part by mass of a catalyst is added, and After stirring and reacting at 20℃～80℃ for 1～10 hours, the temperature is slowly lowered to 0℃～40℃, and then 0.2～8 parts by mass of β-hydroxyethyl methacrylate or pentaerythritol triacrylate or dipentaerythritol pentaacrylate One or more of them, 0.1-1 mass part of polymerization inhibitor hydroquinone and 1-20 mass parts of organic solvent are mixed uniformly and added to it, and after stirring and reacting at 0 ℃ to 40 ℃ for 1 to 8 hours, that is, UV-curable polyurethane resins are available.

Wherein, the polyethylene glycol, polypropylene glycol or polycarbonate diol has a number-average molecular weight of 400-20,000 g/mol; and the hydroxyl-terminated silicone oil has a number-average molecular weight of 400-20,000 g/mol.

Wherein, the organic solvent is selected from one or more of ethyl acetate, butyl acetate, tetrahydrofuran, and acetone; the catalyst is selected from bisdimethylaminoethyl ether, pentamethyldiethylenetriamine, diethylenetriamine One or more of methylcyclohexylamine, dibutyltin dilaurate and N,N'-lutidine.

Wherein, the active diluent is methacrylic acid-β-hydroxyethyl ester, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, isobornyl acrylate and pentaerythritol triacrylate. one or more

Wherein, the preparation steps of the modified nanoparticles are as follows: the mass ratio of fluorosilane and nanoparticles is 0.1-2, put into 50-250 mL of ethanol for high-speed dispersion, and the mass-volume ratio of fluorosilane and ethanol is 4-20 g/L , after the nanoparticles are evenly dispersed, add ammonia water (concentration 28%), and the amount of ammonia water is 3% to 15% of the total mass of fluorosilane and nanoparticles, and then react at 40 ° C to 100 ° C for 6 to 24 hours later, After washing and drying, hydrophobic modified nanoparticles are obtained.

Preferably, the fluorosilane is selected from tridecafluoroalkylpropyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane One or more of the base silanes; the nanoparticles are selected from one or more of alumina, silica, zinc oxide, zirconia and titania, and the particle size is 1-100 nm.

Wherein, the photoinitiator is diethyl 2,4,6-trimethylbenzoylphosphonate, 2-phenyl-2,2-dimethylamino-1-(4-morpholinephenyl)- 1-Butanone, 2-Hydroxy-2-methyl-1-phenyl-1-propanone, α,α-diethoxyacetophenone, 1-hydroxy-cyclohexylbenzophenone and 2,4,6 -At least one of trimethylbenzoyldiphenylphosphine oxide; the auxiliary agent is one or more of a leveling agent, a defoaming agent or an adhesion promoter.

Wherein, the leveling agent is BYK-300, BYK-310, BYK-320, BYK-322, BYK-331, BYK-333, BYK-378, BYK-388, or BYK-UV3510; the Defoamers BYK-065, BYK-070, BYK-077, BYK-085, BYK-088 or BYK-141; Adhesion Promoters BYK-4500, BYK-4509, BYK-4510, BYK-4511, BYK-4512 or one or more of BYK-4513.

The preparation method of the light-curing anti-graffiti coating with self-healing function according to the present invention comprises the following steps: mixing the hydrophobic nano-particles and the reactive diluent, and then adding the UV-curable polyurethane resin and the photoinitiator and The additives are dispersed at a high speed for 10 to 30 minutes under the condition of a rotating speed of 800 to 3000 r/min to obtain a light-curing anti-graffiti coating with self-healing function, which is then packaged for later use.

The application of the light-curing anti-graffiti coating with self-healing function of the present invention in wood, floor, electronic or plastic products.

Since the invention adopts the grafted fluorosilane, the anti-graffiti component fluorosilane in the coating will not be freed, the function is not easily lost, and has high-quality weather resistance and long-term anti-graffiti function. Specifically, the self-healing function of the coating formed after the coating of the present invention is mainly based on the fluorosilane grafted on the nanoparticles, because the nanoparticles are immobile in the coating, but the fluorosilane molecules grafted on the surface thereof are not movable. The segment can migrate to the surface under humid and heat conditions and repair the damaged surface by itself (because the fluorocarbon chain of fluorosilane is a low surface energy substance, oil pollution, etc. will not be compatible with it), so nanoparticles play a role in adjusting The role of the mechanical properties of the coating, on the other hand, it can also fix the fluorosilane molecules so that they are not easily lost to ensure the durability of the anti-graffiti performance of the coating when used outdoors.

The coating beneficial effect of the present invention: compared with the prior art, the present invention has the following advantages:

(1) The preparation process is simple, the cost is low, and it is suitable for large-area construction. It can be applied to the surface of different objects in a variety of ways, without heating and curing, and curing can be completed within 5-30 seconds of UV light, with high efficiency and low energy consumption. ;

(2) After the coating is worn by mechanical external force, the fluorocarbon long chains of the polyurethane resin and modified nanoparticles in the coating can migrate to the surface in a humid and hot environment, so that the damaged part can self-heal in order to restore its anti-graffiti properties. ;

(3) The anti-graffiti paint of the present invention can be effectively applied to the fields of woodware, indoor floor, furniture, electronic and plastic products and the like.

Description of drawings

Figure 1 shows the coating film of oily black pen graffiti wiped clean by toilet paper.

Detailed ways

The present invention will be further described below in conjunction with the embodiments.

The experimental methods described in the examples are conventional methods unless otherwise specified; the reagents and materials can be obtained from commercial sources unless otherwise specified.

Among them: such as titanium dioxide nanoparticles (purchased from Nanjing Poket New Material Co., Ltd., model PTT-P20C)

Silica nanoparticles (purchased from Nanjing Poket New Material Co., Ltd., model PST-Q02)

Zirconium dioxide nanoparticles (purchased from Nanjing Poket New Materials Co., Ltd., model PGT-D30)

Hydroxy-terminated silicone oil (purchased from Shandong Yousuo Chemical Technology Co., Ltd., model PMX-0156)

2-Phenyl-2,2-dimethylamino-1-(4-morpholinephenyl)-1-butanone (purchased from Chongqing Cypronas Technology Co., Ltd., model: photoinitiator)

β-Hydroxyethyl methacrylate (2-hydroxyethyl methacrylate, purchased from Aladdin Biochemical Technology Co., Ltd., model H140643)

Diethyl 2,4,6-trimethylbenzoylphosphonate (purchased from Foshan Pingsheng Chemical Co., Ltd., model TPO)

2-Hydroxy-2-methyl-1-phenyl-1-propanone (purchased from Wuhan Haorong Biotechnology Co., Ltd., model 1173)

Defoamer, leveling agent, and adhesion promoter were purchased from BYK Auxiliary Co., Ltd.; the above-mentioned raw materials can also be purchased from other manufacturers with the same type of products.

Example 1

(1) First add 100 mL of ethanol and 1.2 parts by mass of tridecafluorooctyltriethoxysilane (the mass volume ratio of fluorosilane to ethanol is 12 g/L) in a 250 mL beaker, and then add 9 parts by mass of titanium dioxide after stirring evenly Nanoparticles and 0.6 parts by mass of ammonia water (mass fraction 28%) were sonicated for 10 minutes, stirred and reacted at a temperature of 60° C. for 24 hours, washed and dried to obtain modified titanium dioxide nanoparticles.

(2) 4 parts by mass of isophorone diisocyanate, 7 parts by mass of polyethylene glycol (molecular weight: 400 g/mol) and 8 parts by mass of hydroxyl-terminated fluorine-containing silicone oil (molecular weight: 1000 g/mol) were dissolved in 10 parts by mass A uniform mixed solution was obtained in acetone, 0.2 parts by mass of dibutyltin dilaurate was added, and the reaction was stirred at 60 °C for 4 hours, then slowly cooled to 40 °C, and then 5 parts by mass of pentaerythritol triacrylate, 0.3 parts of polymerization inhibitor p-phenylene The diphenol and 8 parts of acetone are mixed uniformly and then added to the mixture, and the reaction is stirred at 40° C. for 3 hours to obtain a UV-curable polyurethane resin.

(3) Method for preparing anti-graffiti paint: 65 parts by mass of UV-curable polyurethane resin, 15 parts by mass of 1,6-hexanediol diacrylate, 18 parts by mass of modified titanium dioxide nanoparticles, 0.5 part by mass of photoinitiator 2 -Phenyl-2,2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 0.2 parts of leveling agent BYK-300 and 0.5 parts of adhesion promoter BYK-4512 at 2500 rpm/ After dispersing for 30 minutes at a rotating speed of 10 minutes, pack it for later use.

Example 2

(1) First add 130 mL of tetrahydrofuran and 1.5 parts by mass of heptadecafluorodecyltrimethoxysilane (the mass volume ratio of fluorosilane to tetrahydrofuran is 11.5 g/L) in a 250 mL beaker, and then add 8 parts by mass of two Silica nanoparticles and 1 mass part of ammonia water (mass fraction 28%) were sonicated for 10 min, stirred and reacted at a temperature of 65° C. for 24 h, washed and dried to obtain modified silica nanoparticles.

(2) 2 parts by mass of hexamethylene diisocyanate, 9 parts by mass of polycarbonate diol (molecular weight: 1000 g/mol) and 6 parts by mass of hydroxyl-terminated fluorosilicone oil (molecular weight: 2000 g/mol) were dissolved in 20 parts by mass of 0.2 parts by mass of pentamethyldiethylenetriamine was added into the tetrahydrofuran and 0.2 parts by mass of pentamethyldiethylenetriamine was added. After stirring and reacting at 60 ° C for 5 hours, the temperature was slowly lowered to 40 ° C. Then 4 parts by mass of dipentaerythritol pentaacrylate, 0.2 parts by mass of resistance The polymerizing agent hydroquinone and 12 parts of tetrahydrofuran were mixed uniformly and added thereto, and the reaction was stirred at 40° C. for 2 hours to obtain a UV-curable polyurethane resin.

(3) The method for preparing the anti-graffiti coating is as follows: 60 parts by mass of UV-curable polyurethane resin, 18 parts by mass of isobornyl acrylate (isobornyl acrylate), 20 parts by mass of modified silica nanoparticles, 0.6 part by mass of Photoinitiator α,α-diethoxyacetophenone, 0.3 part of leveling agent BYK-333 and 0.5 part of defoamer BYK-070 were dispersed at 2500 rpm for 30 minutes, and then packaged for later use.

Example 3

(1) First add 120 mL of butyl acetate and 2 parts by mass of dodecafluoroheptylpropyl trimethoxysilane (the mass volume ratio of fluorosilane to butyl acetate is 16.7 g/L) in a 250 mL beaker, and after stirring evenly 10 parts by mass of zirconium dioxide nanoparticles and 1.5 parts by mass of ammonia water (28% by mass) were added, and after sonication for 15 minutes, the reaction was stirred at a temperature of 65° C. for 24 hours, washed and dried to obtain modified zirconium dioxide nanoparticles.

(2) 4.5 parts by mass of hexamethylene diisocyanate, 8 parts by mass of polypropylene glycol (molecular weight: 600 g/mol) and 9 parts by mass of hydroxyl-terminated fluorine-containing silicone oil (molecular weight: 1000 g/mol) were dissolved in 15 parts by mass of tetrahydrofuran A uniform mixed solution was obtained, 0.3 parts by mass of N,N'-lutidine was added, and after stirring and reacting at 60 °C for 4 hours, the temperature was slowly lowered to 40 °C, and then 6 parts by mass of β-hydroxyethyl methacrylate were added, 0.1 part of the polymerization inhibitor hydroquinone and 10 parts of tetrahydrofuran were mixed uniformly and added to the mixture, and the reaction was stirred at 40° C. for 2 hours to obtain a UV-curable polyurethane resin.

(3) The method for preparing the anti-graffiti coating is as follows: 55 parts by mass of UV-curable polyurethane resin, 23 parts by mass of pentaerythritol triacrylate, 22 parts by mass of modified zirconium dioxide nanoparticles, 0.5 part by mass of photoinitiator 1-hydroxyl- Cyclohexyl benzophenone, 0.2 part of defoamer BYK-141 and 0.6 part of adhesion promoter BYK-4509 were dispersed at 2500 rpm for 30 minutes, and then packaged for later use.

Example 4

(1) First add 50 mL of ethanol and 1.5 parts by mass of trifluoroalkylpropyltrimethoxysilane (the mass volume ratio of fluorosilane to ethanol is 4 g/L) in a 250 mL beaker, and then add 15 parts by mass after stirring evenly Titanium dioxide nanoparticles and 0.5 parts by mass of ammonia water (mass fraction 28%) were ultrasonicated for 10 minutes, stirred and reacted at a temperature of 40° C. for 24 hours, washed and dried to obtain modified titanium dioxide nanoparticles.

(2) Dissolve 0.2 parts by mass of isophorone diisocyanate, 0.2 parts by mass of polyethylene glycol (molecular weight: 400 g/mol) and 0.2 parts by mass of hydroxyl-terminated fluorine-containing silicone oil (molecular weight: 400 g/mol) in 2 parts by mass A uniform mixed solution was obtained in ethyl acetate, 0.1 part by mass of bisdimethylaminoethyl ether was added, and the reaction was stirred at 20 ° C for 10 hours, then slowly cooled to 0 ° C, and then 0.2 mass part of pentaerythritol triacrylate, 0.1 part of resistance The polymerizing agent hydroquinone and 1 part of ethyl acetate are mixed uniformly and added thereto, and after stirring and reacting at 0° C. for 8 hours, an ultraviolet light-curable polyurethane resin is obtained.

(3) Method for preparing anti-graffiti paint: 10 parts by mass of UV-curable polyurethane resin, 10 parts by mass of 1,6-hexanediol diacrylate, 5 parts by mass of modified titanium dioxide nanoparticles, 0.5 part by mass of photoinitiator 2 -Hydroxy-2-methyl-1-phenyl-1-propanone, 0.05 part of leveling agent BYK-333 and 0.05 part of adhesion promoter BYK-4510 were dispersed at 3000 rpm for 10 minutes before packing for later use .

Example 5

(1) First add 100 mL of ethanol and 2 parts by mass of tridecafluorooctyltriethoxysilane (the mass volume ratio of fluorosilane to ethanol is 20 g/L) in a 250 mL beaker, and then add 1 part by mass of oxidation Aluminum nanoparticles and 0.45 parts by mass of ammonia water (mass fraction 28%) were sonicated for 10 minutes, stirred and reacted at a temperature of 100° C. for 6 hours, washed and dried to obtain modified alumina nanoparticles.

(2) 6 parts by mass of isophorone diisocyanate, 20 parts by mass of polyethylene glycol (molecular weight: 10,000 g/mol) and 12 parts by mass of hydroxyl-terminated fluorine-containing silicone oil (molecular weight: 10,000 g/mol) were dissolved in 20 parts by mass of A uniform mixed solution was obtained in acetone, and 1 part by mass of pentamethyl diethylene triamine was added. After stirring and reacting at 80 ° C for 1 hour, the temperature was slowly lowered to 40 ° C, and then 8 parts by mass of pentaerythritol triacrylate and 1 part of polymerization inhibitor were added. Hydroquinone and 1 part of acetone are mixed uniformly and then added to the mixture, and after stirring and reacting at 30° C. for 5 hours, a UV-curable polyurethane resin is obtained.

(3) Method for preparing anti-graffiti paint: 70 parts by mass of UV-curable polyurethane resin, 40 parts by mass of 1,6-hexanediol diacrylate, 30 parts by mass of modified alumina nanoparticles, and 10 parts by mass of photoinitiator 2-Phenyl-2,2-dimethylamino-1-(4-morpholinephenyl)-1-butanone, 5 parts of leveling agent BYK-388, 2.5 parts of defoamer BYK-065 and 2.5 parts of After the force accelerator BYK-4500 is dispersed at 800 rpm for 30 minutes, it is packaged for later use.

Test Example 1

The coatings of the above-mentioned examples 1 to 3 are sprayed or brushed on the surfaces of substrates such as wood and plastic, and cured into a film (film thickness of 10-50 microns) after 5-30 seconds of UV light, and the paint film is subjected to the following technical properties Test, the performance test results are shown in Figure 1 and Table 1:

Among them, Fig. 1 is the coating film formed in Example 1, the coating film of oily black pen graffiti can be wiped clean with toilet paper, indicating that the coating film has anti-graffiti performance.

In Table 1, (1) see GB/T 6739-2006, GB/T 9286-1998 for the test of hardness and adhesion of the coating; (2) The test of the water contact angle of the coating is measured by a contact angle meter. Larger indicates better hydrophobicity and better anti-graffiti properties; (3) For the tests of salt spray resistance, aging resistance, solvent wiping resistance and liquid medium resistance of the coating, see the national standards in the table; (4) Anti-aging The graffiti test uses water-based and oil-based pollutants to draw a stroke on the coating film, wipe it back and forth with dry toilet paper, and completely eliminate the pen marks as the basis for judging whether the anti-fouling performance is good or bad. 1-20 times are qualified, and more than 20 times are judged. Basically no anti-graffiti properties; (5) After 20kPa pressure sandpaper is worn, heated at 80°C for 10 minutes, and the water contact angle can recover above 90°, it is judged to have self-healing properties; (6) 3M tape is used for the anti-sticking test. Repeatedly paste the coating 50 times to see if there is any residue on the tape. No residue is considered qualified.

The preparation method of Comparative Example 1 is the same as that of Example 1, except that ordinary titanium dioxide nanoparticles are used (without modification with fluorosilane).

Table 1

It can be seen from Table 1 that the anti-graffiti coating of the present invention has excellent properties, and has self-healing properties, which can be effectively used in the fields of wood, indoor floors, furniture, electronic and plastic products, etc. Without the grafted fluorosilane, the hydrophobicity and anti-graffiti properties of the coating were significantly reduced.

Claims (7)

1. a preparation method of the light-curing anti-graffiti paint with self-healing function, is characterized in that, comprises the steps: UV-curable polyurethane resin, reactive diluent, modified nanoparticle, photoinitiator and auxiliary agent The light-curing anti-graffiti coating with self-healing function is obtained after dispersing at high speed for 10-30 minutes under the condition of rotating speed of 800-3000 r/min, and then packaged for later use; The light-curing anti-graffiti coating with self-healing function is prepared by blending UV-curable polyurethane resin, reactive diluent, hydrophobically modified nanoparticles, photoinitiator and auxiliary; wherein the components are in parts by weight It is: 10-70 parts of UV-curable polyurethane resin, 10-40 parts of reactive diluent, 5-30 parts of modified nanoparticles, 0.5-10 parts of photoinitiator, and 0.1-10 parts of auxiliary; the hydrophobic modification Nanoparticles are grafted fluorosilane on nanoparticles; The UV-curable polyurethane resin is composed of 0.2 to 6 parts by mass of one or more of isophorone diisocyanate or hexamethylene diisocyanate, and 0.2 to 20 parts by mass of polyethylene glycol or polypropylene glycol or polyethylene glycol. One or more of carbonate diols and 0.2-12 parts by mass of hydroxyl-terminated fluorine-containing silicone oil are dissolved in 2-20 parts by mass of organic solvent to obtain a uniform mixed solution, and 0.1-1 parts by mass of catalyst are added, and the temperature is 20 ℃～ After stirring and reacting at 80°C for 1 to 10 hours, the temperature was slowly lowered to 0°C to 40°C, and then 0.2 to 8 parts by mass of β-hydroxyethyl methacrylate or pentaerythritol triacrylate or dipentaerythritol pentaacrylate was added. One or several kinds, 0.1-1 mass part of polymerization inhibitor hydroquinone and 1-20 mass parts of organic solvent are mixed uniformly and added to it, and after stirring and reacting at 0 ℃ to 40 ℃ for 1 to 8 hours, can be obtained. UV curable polyurethane resin. 2. the preparation method of the light-curing anti-graffiti paint with self-healing function according to claim 1, is characterized in that, described organic solvent is all from a kind of in ethyl acetate, butyl acetate, tetrahydrofuran, acetone or Several; described catalyst is selected from a kind of in bis-dimethylaminoethyl ether, pentamethyldiethylenetriamine, dimethylcyclohexylamine, dibutyltin dilaurate, N, N'-lutidine or several. 3. The light-curing anti-graffiti coating with self-healing function according to claim 1, wherein the reactive diluent is methacrylic acid-β-hydroxyethyl ester, trimethylolpropane triacrylate, One or more of 1,6-hexanediol diacrylate, isobornyl acrylate and pentaerythritol triacrylate 4. The photocurable anti-graffiti coating with self-healing function according to claim 1, wherein the modified nanoparticle is prepared in the steps of: fluorosilane and nanoparticle, in a mass ratio of 0.1 to 2, Put into 50~250 mL of ethanol for high-speed dispersion, the mass-volume ratio of fluorosilane to ethanol is 4-20 g/L, after the nanoparticles are evenly dispersed, add ammonia water, and the amount of ammonia water is 3% of the total mass of fluorosilane and nanoparticles. %~15%, then react at 40℃~100℃ for 6~24 hours, wash and dry to obtain hydrophobic modified nanoparticles. 5. The photocurable anti-graffiti coating with self-healing function according to claim 4, wherein the fluorosilane is selected from the group consisting of tridecyl propyl trimethoxy silane, dodecyl fluoroheptyl propyl One or more of trimethoxysilane, heptadecafluorodecyltrimethoxysilane, and tridecafluorooctyltrimethoxysilane; the nanoparticles are selected from: alumina, silica, zinc oxide, One or more of zirconia and titania, with a particle size of 1 to 100 nm. 6. The photocurable anti-graffiti coating with self-healing function according to claim 1, wherein the photoinitiator is diethyl 2,4,6-trimethylbenzoylphosphonate, 2 -Phenyl-2,2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, α,α- At least one of diethoxyacetophenone, 1-hydroxy-cyclohexyl benzophenone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; the auxiliary agent is the auxiliary agent It is one or more of a leveling agent, an antifoaming agent or an adhesion promoter. 7. Application of the light-curing anti-graffiti paint with self-healing function prepared by the preparation method of claim 1 in wood, floor, electronic or plastic products.

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