阅读说明：本技术 一种水性uv漆及其配制方法 (Water-based UV paint and preparation method thereof ) 是由 吴浩 关存州 于 2021-05-31 设计创作，主要内容包括：本发明公开了一种水性UV漆及其配制方法,属于UV漆制造技术领域,该种水性UV漆包括以下重量份的原料:超支化聚氨酯丙烯酸酯乳液20-40份、改性丙烯酸酯乳液20-40份、无水乙醇15-25份、乙二醇丁醚5-15份、滑石粉5-10份、光引发剂1-5份、消泡剂0.1-0.5份、胺中和剂0.1-0.5份。且本发明合成了具有高度支化结构的超支化聚氨酯丙烯酸酯,且该分子中含有大量的末端丙烯酸酯基和封端的双键,协同提供高了UV固化速度,减短UV固化时间；本发明提供的水性UV漆,具有优良的附着力和硬度,且获得漆膜具有优良的机械强度,以及优良的耐水性、耐油性和耐污性。(The invention discloses a water-based UV paint and a preparation method thereof, belonging to the technical field of UV paint manufacture, wherein the water-based UV paint comprises the following raw materials, by weight, 20-40 parts of hyperbranched polyurethane acrylate emulsion, 20-40 parts of modified acrylate emulsion, 15-25 parts of absolute ethyl alcohol, 5-15 parts of ethylene glycol monobutyl ether, 5-10 parts of talcum powder, 1-5 parts of photoinitiator, 0.1-0.5 part of defoaming agent and 0.1-0.5 part of amine neutralizer. The hyperbranched polyurethane acrylate with a highly branched structure is synthesized, and the molecule contains a large amount of terminal acrylate groups and terminated double bonds, so that the UV curing speed is improved, and the UV curing time is shortened; the water-based UV paint provided by the invention has excellent adhesion and hardness, and the obtained paint film has excellent mechanical strength, water resistance, oil resistance and stain resistance.)

1. The water-based UV paint is characterized by comprising the following raw materials, by weight, 20-40 parts of hyperbranched polyurethane acrylate emulsion, 20-40 parts of modified acrylate emulsion, 15-25 parts of absolute ethyl alcohol, 5-15 parts of butyl cellosolve, 5-10 parts of talcum powder, 1-5 parts of photoinitiator, 0.1-0.5 part of defoaming agent and 0.1-0.5 part of amine neutralizer;

the hyperbranched polyurethane acrylate emulsion is prepared by the following steps:

step A, stirring hexamethylene diisocyanate and N, N-dimethylformamide uniformly, heating the temperature of a reaction system to 73 ℃ in a nitrogen atmosphere, then dropwise adding an N, N-dimethylformamide solution containing terephthalic acid and a catalyst A, measuring the NCO value of the reaction system every 20min after dropwise adding, heating the temperature of the reaction system to 77 ℃ when the NCO value reaches 15.01%, dropwise adding glycerol, measuring the NCO value of the reaction system every 20min after dropwise adding, stopping heating, washing with water, and drying in vacuum when the NCO value is lower than 1%, thus obtaining an intermediate 1;

b, stirring hexamethylene diisocyanate and N, N-dimethylformamide uniformly, heating the reaction system to 43 ℃ in the nitrogen atmosphere, then dropwise adding an N, N-dimethylformamide solution containing hydroxypropyl acrylate, a catalyst B and a polymerization inhibitor, measuring the NCO value of the reaction system every 20min after dropwise adding, and stopping heating and washing when the NCO value reaches 12.82% to obtain an intermediate 2;

step C, uniformly stirring the intermediate 1 and the N, N-dimethylformamide obtained in the step A, heating the reaction system to 67 ℃ in a nitrogen atmosphere, dropwise adding an N, N-dimethylformamide solution containing the intermediate 2 and a catalyst C, measuring the NCO value of the reaction system every 20min after dropwise adding, and stopping heating, washing and drying when the NCO value is less than 0.5% to obtain hyperbranched polyurethane acrylate;

and D, dissolving an emulsifier in deionized water, dropwise adding the hyperbranched polyurethane acrylate obtained in the step C at normal temperature for 30-50min, and mechanically stirring for 15-25min after complete dropwise addition to obtain the hyperbranched polyurethane acrylate emulsion.

2. The aqueous UV paint according to claim 1, wherein in the step A, the ratio of the hexamethylene diisocyanate to the N, N-dimethylformamide solution containing the terephthalic alcohol and the catalyst A to the glycerol is 0.2-0.23mol:10-25mL:20mL:0.12-0.14mol, the molar concentration of the terephthalic alcohol in the N, N-dimethylformamide solution containing the terephthalic alcohol and the catalyst A is 4.8-5mol/L, and the mass concentration of the catalyst A is 1-1.6 g/L.

3. The aqueous UV paint according to claim 1, wherein the amount ratio of the hexamethylene diisocyanate, N-dimethylformamide and the N, N-dimethylformamide solution containing hydroxypropyl acrylate and catalyst B in step B is 0.1-0.13mol:13-26mL:25mL, the molar concentration of hydroxypropyl acrylate in the N, N-dimethylformamide solution containing hydroxypropyl acrylate, catalyst B and polymerization inhibitor is 5-5.2mol/L, the mass concentration of catalyst B is 0.5-1.5g/L, and the mass concentration of polymerization inhibitor is 1.5-2 g/L.

4. The aqueous UV paint according to claim 1, wherein the amount ratio of the intermediate 1, N-dimethylformamide and the N, N-dimethylformamide solution containing the intermediate 2 and the catalyst C in the step C is 0.1-0.13mol:15-25mL:10-13mL, the molar mass concentration of the intermediate 2 in the N, N-dimethylformamide solution containing the intermediate 2 and the catalyst C is 1mol/L, and the mass concentration of the catalyst C is 0.5-1.5 g/L; and D, the mass ratio of the emulsifier, the deionized water and the hyperbranched polyurethane acrylate in the step D is 0.6-1.5:13-23: 20-35.

5. The aqueous UV paint of claim 1, wherein the modified acrylate emulsion is prepared by the following steps:

e1, dissolving the emulsifier in deionized water, dropwise adding ethyl acrylate into the solution at room temperature under stirring for 30-50min, and finally stirring at 900-1200r/min for 20-30min to obtain ethyl acrylate emulsion;

e2, under the protection of nitrogen, uniformly stirring methyl methacrylate, ethyl acrylate, dodecafluoroheptyl methacrylate and ammonium persulfate, heating the temperature of a reaction system to 81 ℃, keeping the temperature for reaction for 20min, dropwise adding 1/2 parts of ethyl acrylate emulsion, stirring for reaction for 1-2h, dropwise adding the rest part of ethyl acrylate emulsion, stirring for reaction for 1.5-2.5h, then adding 3-isocyanatopropyltriethoxysilane, heating the temperature of the reaction system to 85 ℃, stirring for reaction for 1-1.5h, cooling to 30 ℃, and filtering the emulsion by using a filter screen to obtain the modified acrylate emulsion.

6. The method for formulating an aqueous UV paint according to claim 1, comprising the steps of:

mixing and stirring the hyperbranched polyurethane acrylate emulsion and the modified acrylate emulsion for 8-15 minutes, then adding talcum powder, mixing and stirring for 18-23 minutes, then adding the defoaming agent while stirring, stirring for 8-15 minutes, finally sequentially adding the photoinitiator and the amine neutralizer, stirring for 8-15 minutes after completely adding, and filtering by using a filter screen to obtain the water-based UV paint.

Technical Field

The invention belongs to the technical field of UV paint manufacturing, and particularly relates to a water-based UV paint and a preparation method thereof.

Background

The UV paint generally refers to a photo-curable coating, which is also called a photo-sensitive coating, and is also called an ultraviolet light-curable coating, which uses ultraviolet light as a coating curing energy. It features that it can be quickly solidified to form film on the inflammable substrate of paper, plastics, leather and wood, etc. without heating. The water-based UV paint is a photocuring paint taking water as a diluent, does not contain an organic solvent, is green and environment-friendly, combines the advantages of a water-based paint and a photocuring paint, and is developed rapidly in recent years.

But the performance of the current water-based UV paint has the following defects of insufficient adhesive force and hardness; the drying speed is too slow; the performance (such as abrasion resistance, water resistance and oxygen resistance) of the obtained composite film is not high.

Publication No. CN104804498A discloses a water-based UV paint for plastics, which comprises the following components, by weight, 25-50 parts of epoxy modified acrylic resin; 10-25 parts of active diluent; 1-4 parts of a photoinitiator; 5-15 parts of a solvent; 0-7 parts of a flatting agent; 1-2 parts of a dispersant; 0-2 parts of thickening agent; 5-15 parts of water; 0.2-1 part of defoaming agent; 0.2-1 part of flatting agent; 1-3 parts of adhesion promoter; the adhesion promoter is a phenoxy dimethyl silane compound; the interlayer adhesion of the water-based UV paint to a plastic substrate can be improved by matching the epoxy modified acrylic resin with the adhesion promoter of which the component is a phenoxy dimethyl silane compound. However, the aqueous UV paint has a problem of slow film-forming drying speed.

The application number CN201110258320.3 discloses a water-based UV paint and a preparation method thereof, and the water-based UV paint comprises the following components, by weight, water-based aliphatic polyurethane Neorad R44448-15%, water-based aliphatic polyurethane Neorad R44740-55%, water-based acrylic prepolymer Neorad R44810-20%, an initiator 2-6%, a water-based UV leveling agent 0.5-1.5%, and a water-based UV defoaming agent 0.5-1.0%. However, the above aqueous UV paint has a problem that the water resistance of the film after film formation is insufficient.

Therefore, the invention provides the water-based UV paint and the preparation method thereof, which can improve the adhesive force and the hardness of the water-based UV paint, shorten the UV curing time and shorten the drying time of the UV paint.

Disclosure of Invention

The invention aims to provide a water-based UV paint and a preparation method thereof, and aims to solve the problems of insufficient adhesive force and hardness, slow drying speed and insufficient water resistance of a paint film of the water-based UV paint.

The invention can be realized by the following technical scheme:

the water-based UV paint comprises, by weight, 20-40 parts of hyperbranched polyurethane acrylate emulsion, 20-40 parts of modified acrylate emulsion, 15-25 parts of absolute ethyl alcohol, 5-15 parts of butyl cellosolve, 5-10 parts of talcum powder, 1-5 parts of a photoinitiator, 0.1-0.5 part of a defoaming agent and 0.1-0.5 part of an amine neutralizer.

The hyperbranched polyurethane acrylate emulsion is prepared by the following steps:

step A, adding hexamethylene diisocyanate and N, N-dimethylformamide into a four-neck flask provided with a stirring rod, a reflux condenser and nitrogen, uniformly stirring, heating the temperature of the reaction system to 73 ℃ by using an oil bath kettle in the nitrogen atmosphere, dropwise adding an N, N-dimethylformamide solution containing the p-xylene and the catalyst A by using a constant-pressure dropping funnel, measuring the NCO value of the reaction system at intervals of 20min after dropwise adding is finished, heating the reaction system to 77 ℃ when the NCO value reaches 15.01%, dropwise adding glycerol by using a constant-pressure dropping funnel, measuring the NCO value of the reaction system every 20min after the dropwise adding is finished, when the NCO value is lower than 1%, stopping heating, cooling to room temperature, washing for 3-5 times, and drying at 40 ℃ in a vacuum drying oven to obtain an intermediate 1, wherein the reaction process is shown as follows;

step B, adding hexamethylene diisocyanate and N, N-dimethylformamide into a four-neck flask provided with a stirring rod, a condensation pipe and nitrogen, uniformly stirring, heating the temperature of the reaction system to 43 ℃ by using an oil bath kettle in the nitrogen atmosphere, slowly dropwise adding an N, N-dimethylformamide solution containing hydroxypropyl acrylate, a catalyst B and a polymerization inhibitor by using a constant-pressure dropping funnel, measuring the NCO value of the reaction system every 20min after dropwise adding is finished, stopping heating when the NCO value reaches 12.82%, cooling to room temperature, washing for 3-5 times to obtain an intermediate 2, wherein the reaction formula is shown as follows;

step C, adding the intermediate 1, the N, N-dimethylformamide obtained in the step A into a four-neck flask provided with a stirring rod, a condensation pipe and nitrogen, uniformly stirring, heating the reaction system to 67 ℃ by using an oil bath kettle in the nitrogen atmosphere, slowly dropwise adding an N, N-dimethylformamide solution containing the intermediate 2 and a catalyst C by using a constant-pressure dropping funnel, measuring the NCO value of the reaction system every 20min after dropwise adding is finished, stopping heating when the NCO value is less than 0.5%, cooling to room temperature, washing for 3-5 times, and drying at 40 ℃ in a vacuum drying oven to obtain hyperbranched polyurethane acrylate;

and D, dissolving an emulsifier in deionized water, slowly dropwise adding the hyperbranched polyurethane acrylate obtained in the step C at normal temperature and 300r/min for 30-50min, and mechanically stirring for 15-25min after complete dropwise addition to obtain the hyperbranched polyurethane acrylate emulsion.

Furthermore, in the step A, hexamethylene diisocyanate, N-dimethylformamide, an N, N-dimethylformamide solution containing p-xylene and a catalyst A and glycerol are used in a ratio of 0.2-0.23mol:10-25mL:20mL:0.12-0.14mol, the molar concentration of p-xylene in the N, N-dimethylformamide solution containing p-xylene and the catalyst A is 4.8-5mol/L, and the mass concentration of the catalyst A is 1-1.6 g/L.

Further, the catalyst A is triethylamine.

Furthermore, in the step B, the dosage ratio of the hexamethylene diisocyanate to the N, N-dimethylformamide solution containing the hydroxypropyl acrylate and the catalyst B is 0.1-0.13mol:13-26mL:25mL, and in the N, N-dimethylformamide solution containing the hydroxypropyl acrylate, the catalyst B and the polymerization inhibitor, the molar concentration of the hydroxypropyl acrylate is 5-5.2mol/L, the mass concentration of the catalyst B is 0.5-1.5g/L, and the mass concentration of the polymerization inhibitor is 1.5-2 g/L.

Further, the catalyst B is dibutyltin dilaurate.

Further, the polymerization inhibitor is hydroquinone.

Furthermore, the dosage ratio of the intermediate 1, the N, N-dimethylformamide and the N, N-dimethylformamide solution containing the intermediate 2 and the catalyst C in the step C is 0.1-0.13mol:15-25mL:10-13mL, the molar mass concentration of the intermediate 2 in the N, N-dimethylformamide solution containing the intermediate 2 and the catalyst C is 1mol/L, and the mass concentration of the catalyst C is 0.5-1.5 g/L.

Further, catalyst C was dibutyltin dilaurate.

And further, in the step D, the mass ratio of the emulsifier to the deionized water to the hyperbranched polyurethane acrylate is 0.6-1.5:13-23:20-35, and the emulsifier is sodium dodecyl sulfate.

The modified acrylate emulsion is prepared by the following steps:

e1, dissolving the emulsifier in deionized water, dropwise adding ethyl acrylate into the solution at room temperature under stirring for 30-50min, and finally stirring at the speed of 900-1200r/min for 20-30min to obtain ethyl acrylate emulsion;

step E2, under the protection of nitrogen, putting the mixture into a four-neck flask provided with a stirrer, a condenser tube and a nitrogen introducing device, sequentially adding methyl methacrylate, ethyl acrylate, dodecafluoroheptyl methacrylate and ammonium persulfate, stirring uniformly, heating the reaction system to 81 ℃, keeping the temperature for reaction for 20min, slowly dripping 1/2 parts of ethyl acrylate emulsion by using a dropping funnel for 40-60min, stirring for reaction for 1-2h, then slowly dripping the rest part of the ethyl acrylate emulsion by using a dropping funnel for 40-60min, stirring for reacting for 1.5-2.5h, then adding 3-isocyanate propyl triethoxy silane, heating the temperature of the reaction system to 85 ℃, stirring at 400r/min for reaction for 1-1.5h, cooling to 30 ℃, filtering the emulsion by a 200-mesh filter screen, and discharging to obtain the modified acrylate emulsion.

Further, in the step E1, the mass ratio of the emulsifier to the ethyl acrylate to the deionized water is 0.1-0.7:10-20:5-12, and the emulsifier is sodium dodecyl sulfate.

Further, in the step E2, the mass ratio of methyl methacrylate, ethyl acrylate, dodecafluoroheptyl methacrylate, ammonium persulfate, ethyl acrylate emulsion and 3-isocyanatopropyltriethoxysilane is 20-35:7-15:9-16:0.6-1.7:1-1.3: 1.5-3.5.

The photoinitiator is one or a mixture of two of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone and 1-hydroxycyclohexyl phenyl methyl in any ratio.

The defoaming agent is organic silicone oil.

The amine neutralizer is one or a mixture of more of ethanolamine, dimethylethanolamine and amino methyl propanol in any ratio.

A preparation method of a water-based UV paint comprises the following steps:

mixing and stirring the hyperbranched polyurethane acrylate emulsion and the modified acrylate emulsion for 8-15 minutes, then adding talcum powder, mixing and stirring for 18-23 minutes, then adding the defoaming agent while stirring, stirring for 8-15 minutes, finally sequentially adding the photoinitiator and the amine neutralizer, stirring for 8-15 minutes after completely adding, and filtering by using a 300-mesh filter screen to obtain the water-based UV paint.

The invention has the beneficial effects that:

1. the invention synthesizes monomer with polyhydroxy end capping, namely intermediate 1, by using hexamethylene diisocyanate, p-xylene and glycerol, polymerizes monomer with isocyanate group and double bond, namely intermediate 2, then utilizes intermediate 1 and intermediate 2 to carry out polymerization reaction, and forms hyperbranched polyurethane acrylate with a highly branched structure, which has excellent flexibility, weather resistance and adhesive force, and the hyperbranched polyurethane acrylate contains a large number of terminal acrylate groups and end capping double bonds, and the terminal acrylate groups are favorable for improving the maximum conversion rate of the double bonds in the UV curing process, and the larger conversion rate of the double bonds and a large number of end capping double bonds, and the synergistic effect provides high UV curing speed and shortens UV curing time; the hyperbranched polyurethane acrylate takes hexamethylene diisocyanate as a raw material and is aliphatic isocyanate, compared with aromatic diisocyanate chains, the hyperbranched polyurethane acrylate has high flexibility, is favorable for improving the rheological property of hyperbranched polyurethane and reducing the viscosity of a system, is favorable for film formation of the hyperbranched polyurethane acrylate, and shortens the UV curing time; the molecular structure of the hyperbranched polyurethane acrylate contains a large number of rigid groups, namely phenyl, so that the thermodynamic stability and the mechanical strength of a UV curing film are improved; finally, the hyperbranched polyurethane acrylate is prepared into hyperbranched polyurethane acrylate emulsion, so that the dispersion of the hyperbranched polyurethane acrylate in water is promoted, the subsequent full contact between the hyperbranched polyurethane acrylate and other raw materials is facilitated, and the uniformity of the film after film formation is improved.

2. According to the invention, methyl methacrylate, ethyl acrylate and dodecafluoroheptyl methacrylate are used as monomers, the emulsion polymerization principle is utilized to synthesize fluorine modified polyacrylate, 3-isocyanatopropyltriethoxysilane is utilized to graft and modify the fluorine modified polyacrylate, so that a suspended silica chain is grafted on a molecular chain of the obtained polyacrylate, the fluidity of the fluorine modified polyacrylate is promoted, the subsequent UV curing film forming is promoted, the UV curing time is shortened, meanwhile, the addition of the fluorine monomer can improve the oxidation resistance of a polymer chain segment, the weather resistance, temperature change resistance and durability of a paint film are greatly improved, the formed paint film has extremely low surface energy, and the paint film has high water resistance, oil resistance, stain resistance and other properties.

Therefore, the water-based UV paint provided by the invention has excellent adhesion and hardness, shortens the UV curing time, shortens the drying time of a paint film, and obtains the paint film with excellent thermodynamic stability, mechanical strength, water resistance, oil resistance and stain resistance.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1:

the hyperbranched polyurethane acrylate emulsion is prepared by the following steps:

step A, adding hexamethylene diisocyanate and N, N-dimethylformamide into a four-neck flask provided with a stirring rod, a reflux condenser tube and nitrogen, uniformly stirring, heating the temperature of a reaction system to 73 ℃ by using an oil bath kettle in the nitrogen atmosphere, dropwise adding an N, N-dimethylformamide solution containing p-xylene and a catalyst A by using a constant-pressure dropping funnel, measuring the NCO value of the reaction system every 20min after dropwise adding, heating the temperature of the reaction system to 77 ℃ when the NCO value reaches 15.01%, dropwise adding glycerol by using the constant-pressure dropping funnel, measuring the NCO value of the reaction system every 20min after dropwise adding, cooling to room temperature water for washing for 3 times when the NCO value is lower than 1%, and drying at 40 ℃ in a vacuum drying box to obtain an intermediate 1;

b, adding hexamethylene diisocyanate and N, N-dimethylformamide into a four-neck flask provided with a stirring rod, a condensation pipe and nitrogen, uniformly stirring, heating the temperature of the reaction system to 43 ℃ by using an oil bath kettle in the nitrogen atmosphere, slowly dropwise adding an N, N-dimethylformamide solution containing hydroxypropyl acrylate, a catalyst B and a polymerization inhibitor by using a constant-pressure dropping funnel, measuring the NCO value of the reaction system every 20min after dropwise adding is finished, stopping heating when the NCO value reaches 12.82%, cooling to room temperature, washing for 3 times, and obtaining an intermediate 2;

step C, adding the intermediate 1, the N, N-dimethylformamide obtained in the step A into a four-neck flask provided with a stirring rod, a condensation pipe and nitrogen, uniformly stirring, heating the reaction system to 67 ℃ by using an oil bath kettle in the nitrogen atmosphere, slowly dropwise adding an N, N-dimethylformamide solution containing the intermediate 2 and a catalyst C by using a constant-pressure dropping funnel, measuring the NCO value of the reaction system every 20min after dropwise adding is finished, stopping heating when the NCO value is less than 0.5%, cooling to room temperature for washing for 3 times, and drying at 40 ℃ in a vacuum drying oven to obtain hyperbranched polyurethane acrylate;

and D, dissolving an emulsifier in deionized water, slowly dropwise adding the hyperbranched polyurethane acrylate obtained in the step C at normal temperature and 300r/min for 30min, and mechanically stirring for 15-25min after complete dropwise addition to obtain the hyperbranched polyurethane acrylate emulsion.

The raw materials and the amounts of the raw materials used in the respective steps are shown in table 1.

TABLE 1

Example 2:

the hyperbranched urethane acrylate emulsion was prepared by following steps, referring to the preparation steps of example 1, and the raw materials and the amounts of the raw materials used in the respective steps are shown in table 2.

TABLE 2

Example 3:

the hyperbranched urethane acrylate emulsion was prepared by following steps, referring to the preparation steps of example 1, and the raw materials and the amounts of the raw materials used in the respective steps are shown in table 3.

TABLE 3

Example 4:

the modified acrylate emulsion is prepared by the following steps:

e1, dissolving an emulsifier in deionized water, dropwise adding ethyl acrylate into the solution at room temperature under stirring for 30min, and finally stirring at 900r/min for 20min to obtain an ethyl acrylate emulsion, wherein the emulsifier is sodium dodecyl sulfate;

step E2, under the protection of nitrogen, putting the mixture into a four-neck flask provided with a stirrer, a condenser tube and a nitrogen introducing device, sequentially adding methyl methacrylate, ethyl acrylate, dodecafluoroheptyl methacrylate and ammonium persulfate, stirring uniformly, heating the reaction system to 81 ℃, keeping the temperature for reaction for 20min, slowly dripping 1/2 parts of ethyl acrylate emulsion by using a dropping funnel, wherein the dripping time is 40min, stirring for reaction for 1h, then slowly dripping the rest part of the ethyl acrylate emulsion by using a dropping funnel for 40min, stirring for reacting for 1.5h, then adding 3-isocyanate propyl triethoxy silane, heating the temperature of the reaction system to 85 ℃, stirring and reacting for 1h at the speed of 400r/min, cooling to 30 ℃, filtering the emulsion by a 200-mesh filter screen, and discharging to obtain the modified acrylate emulsion.

The raw materials and the amounts of the raw materials used in the respective steps are shown in Table 4.

TABLE 4

Example 5:

the modified acrylate emulsion is prepared by the following steps:

e1, dissolving an emulsifier in deionized water, dropwise adding ethyl acrylate into the solution at room temperature under stirring for 50min, and finally stirring at 1200r/min for 30min to obtain an ethyl acrylate emulsion, wherein the emulsifier is sodium dodecyl sulfate;

step E2, under the protection of nitrogen, putting the mixture into a four-neck flask provided with a stirrer, a condenser tube and a nitrogen introducing device, sequentially adding methyl methacrylate, ethyl acrylate, dodecafluoroheptyl methacrylate and ammonium persulfate, stirring uniformly, heating the reaction system to 81 ℃, keeping the temperature for reaction for 20min, slowly dripping 1/2 parts of ethyl acrylate emulsion by using a dropping funnel, wherein the dripping time is 60min, stirring for reaction for 2h, then slowly dripping the rest part of the ethyl acrylate emulsion by using a dropping funnel for 60min, stirring for reacting for 2.5h, then adding 3-isocyanate propyl triethoxy silane, heating the temperature of the reaction system to 85 ℃, stirring and reacting for 1.5h at the speed of 400r/min, cooling to 30 ℃, filtering the emulsion by a 200-mesh filter screen, and discharging to obtain the modified acrylate emulsion.

The raw materials and the amounts of the raw materials used in the respective steps are shown in Table 5.

TABLE 5

Example 6:

the water-based UV paint comprises the following raw materials, by weight, 20 parts of hyperbranched polyurethane acrylate emulsion, 20 parts of modified acrylate emulsion, 15 parts of absolute ethyl alcohol, 5 parts of butyl cellosolve, 5 parts of talcum powder, 1 part of photoinitiator, 0.1 part of defoaming agent and 0.1 part of amine neutralizer, wherein the photoinitiator is 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone; the defoaming agent is organic silicone oil; the amine neutralizer is ethanolamine; a hyperbranched urethane acrylate emulsion was prepared as in example 1, and a modified acrylate emulsion was prepared as in example 4;

the water-based UV paint is prepared by the following steps:

mixing and stirring the hyperbranched polyurethane acrylate emulsion and the modified acrylate emulsion for 10 minutes, then adding talcum powder, mixing and stirring for 20 minutes, then adding the defoaming agent while stirring, stirring for 12 minutes, finally sequentially adding the photoinitiator and the amine neutralizer, stirring for 13 minutes after completely adding, and filtering by using a 300-mesh filter screen to obtain the water-based UV paint.

Example 7:

the water-based UV paint comprises the following raw materials, by weight, 30 parts of hyperbranched polyurethane acrylate emulsion, 30 parts of modified acrylate emulsion, 20 parts of absolute ethyl alcohol, 10 parts of butyl cellosolve, 7 parts of talcum powder, 3 parts of a photoinitiator, 0.3 part of a defoaming agent and 0.3 part of an amine neutralizer, wherein the photoinitiator is 1-hydroxycyclohexyl phenyl methyl; the defoaming agent is organic silicone oil; the amine neutralizer is dimethylethanolamine; hyperbranched polyurethane acrylate emulsion was prepared as in example 2, and modified acrylate emulsion was prepared as in example 5;

this waterborne UV paint was prepared by the preparation procedure referred to example 6.

Example 8:

the water-based UV paint comprises the following raw materials, by weight, 40 parts of hyperbranched polyurethane acrylate emulsion, 40 parts of modified acrylate emulsion, 25 parts of absolute ethyl alcohol, 15 parts of butyl cellosolve, 10 parts of talcum powder, 5 parts of photoinitiator, 0.5 part of defoaming agent and 0.5 part of amine neutralizer, wherein the photoinitiator is a mixture of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone and 1-hydroxycyclohexyl phenyl methyl according to the mass ratio of 1: 1; the defoaming agent is organic silicone oil; the amine neutralizer is a mixture of dimethylethanolamine and amino methyl propanol which are mixed according to the mass ratio of 1: 1; a hyperbranched urethane acrylate emulsion was prepared as in example 3, and a modified acrylate emulsion was prepared as in example 5;

this waterborne UV paint was prepared by the preparation procedure referred to example 6.

Comparative example 1:

the water-based UV paint comprises the following raw materials, by weight, 20 parts of modified acrylate emulsion, 15 parts of absolute ethyl alcohol, 5 parts of ethylene glycol butyl ether, 5 parts of talcum powder, 1 part of a photoinitiator, 0.1 part of a defoaming agent and 0.1 part of an amine neutralizer, wherein the photoinitiator is 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone; the defoaming agent is organic silicone oil; the amine neutralizer is ethanolamine; a modified acrylate emulsion was prepared for example 4;

this waterborne UV paint was prepared by the preparation procedure referred to example 6.

Comparative example 2:

the water-based UV paint comprises the following raw materials, by weight, 30 parts of hyperbranched polyurethane acrylate emulsion, 20 parts of absolute ethyl alcohol, 10 parts of butyl cellosolve, 7 parts of talcum powder, 3 parts of photoinitiator and 0.3 part of defoaming agent; 0.3 part of amine neutralizer, wherein the photoinitiator is 1-hydroxycyclohexyl phenyl methyl; the defoaming agent is organic silicone oil; the amine neutralizer is dimethylethanolamine; hyperbranched urethane acrylate emulsion was prepared as in example 2;

this waterborne UV paint was prepared by the preparation procedure referred to example 6.

Example 9:

the aqueous UV paints obtained in examples 6 to 8 and comparative examples 1 to 2 were subjected to the following performance tests:

the adhesion is measured according to GB/T9286-1998 standard; the pencil hardness is determined according to the GB/T6739-; flexibility measured according to GB/T1731 + 1993 standard; the water resistance is determined according to the GB/T1733 + 1993 standard; stain resistance, tested according to the specification of 8.2.1 in GB/T9780-2005; measuring the water contact angle by using an SL200B contact angle measuring instrument of Shanghai Clontech information technology Limited, dripping deionized water on the surface of the coated glass plate to be tested, measuring 5 points of each sample, and taking the arithmetic mean value; the drying time of the paint film is determined according to the GB/T1728-1989 standard.

The test results are shown in Table 6.

TABLE 6

As can be seen from the above data, the drying time of the aqueous UV paints obtained in examples 6 to 8 is shorter than that of comparative examples 1 to 2, and the pencil hardness, flexibility, water resistance, and stain resistance of the aqueous UV paints obtained in examples 6 to 8 are superior to those of comparative examples 1 to 2.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.