阅读说明：本技术 改性纳米银粒子及其制备方法、硅烷类化合物及其制备方法、防污涂料及其制备方法 (Modified nano silver particles and preparation method thereof, silane compound and preparation method thereof, antifouling paint and preparation method thereof ) 是由 宋光铃 邓雅君 郑大江 于 2019-10-11 设计创作，主要内容包括：本发明提供一种改性纳米银粒子及其制备方法。所述改性纳米银粒子为树莓状结构,包括作为内核的纳米银粒子以及包覆在所述纳米银粒子外的单宁酸壳层,所述单宁酸壳层的表面负载纳米二氧化硅颗粒。本发明还提供一种硅烷类化合物及其制备方法。所述硅烷类化合物通过将甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯、γ-甲基丙烯酰氧基丙基三甲氧基硅烷和(3-氨丙基)三乙氧基硅烷在引发剂的引发下反应得到。本发明还提供一种防污涂料及其制备方法。所述防污涂料包括上述改性纳米银粒子和上述硅烷类化合物中的至少一种。改性纳米银粒子能够控制银离子的释放可控性,并改善银粒子与涂层的相容性,提高防污涂料的防污效果,减少对海洋环境的污染和破坏。(The invention provides a modified nano silver particle and a preparation method thereof. The modified nano silver particles are of raspberry-shaped structures and comprise nano silver particles serving as inner cores and tannin shell layers coated outside the nano silver particles, and nano silicon dioxide particles are loaded on the surfaces of the tannin shell layers. The invention also provides a silane compound and a preparation method thereof. The silane compound is obtained by reacting glycidyl methacrylate, hydroxyethyl methacrylate, gamma-methacryloxypropyltrimethoxysilane and (3-aminopropyl) triethoxysilane under the initiation of an initiator. The invention also provides an antifouling paint and a preparation method thereof. The antifouling paint comprises at least one of the modified nano silver particles and the silane compound. The modified nano silver particles can control the release controllability of silver ions, improve the compatibility of the silver particles and a coating, improve the antifouling effect of the antifouling paint, and reduce the pollution and damage to the marine environment.)

1. The modified nano-silver particle is characterized in that the modified nano-silver particle is of a raspberry-shaped structure and comprises a nano-silver particle serving as an inner core and a tannic acid shell layer coated outside the nano-silver particle, and nano silicon dioxide particles are loaded on the surface of the tannic acid shell layer.

2. The modified nanosilver particles of claim 1, wherein the modified nanosilver particles are obtained by reacting nanosilver particles with tannic acid, ethyl orthosilicate;

the silver nanoparticles are prepared by reacting silver nitrate and polyvinylpyrrolidone in ethylene glycol;

wherein the mass ratio of the silver nitrate to the polyvinylpyrrolidone, the glycol, the tannic acid and the ethyl orthosilicate is 0.1-2: 0.05-10: 10-500: 0.1-2: 0.005-0.20; preferably 0.5 to 2: 0.1-10: 50-250: 0.5-1.5: 0.015-0.06.

3. A method for preparing modified silver nanoparticles, for preparing the modified silver nanoparticles of any one of claims 1-2, comprising the steps of:

step 10, reacting silver nitrate and polyvinylpyrrolidone in ethylene glycol to obtain nano silver particles;

step 20, dispersing the nano silver particles obtained in the step 10 in ethanol, adding an ethanol solution of tannic acid for reaction to obtain tannic acid modified nano silver particles with a core-shell structure;

and step 30, dispersing the nano silver particles with the core-shell structure modified by the tannic acid obtained in the step 20 in ethanol, adding water, and then adding an ethanol solution of ethyl orthosilicate for reaction to obtain the modified nano silver particles.

4. The silane compound is characterized by being obtained by reacting glycidyl methacrylate, hydroxyethyl methacrylate, gamma-methacryloxypropyltrimethoxysilane and (3-aminopropyl) triethoxysilane under the initiation of an initiator.

5. The silane compound according to claim 4, wherein the molar ratio of the glycidyl methacrylate, the hydroxyethyl methacrylate, the γ -methacryloxypropyltrimethoxysilane, and the (3-aminopropyl) triethoxysilane is 1 to 9: 1-9: 1-6: 1-3; preferably 1 to 6: 1-3: 2-4: 1-2.

6. The silane compound according to claim 4, wherein the initiator is azobisisobutyronitrile; the mass percentage of the azodiisobutyronitrile in the reaction system is 0.01-10 wt%;

preferably, the mass ratio of the azobisisobutyronitrile in the reaction system is 0.1 to 5 wt%.

7. A method for producing a silane compound, which is used for producing the silane compound according to any one of claims 4 to 6, comprising the steps of:

step 40, reacting glycidyl methacrylate, hydroxyethyl methacrylate and gamma-methacryloxypropyl trimethoxysilane under the initiation of an initiator to obtain an intermediate compound;

and step 50, reacting the intermediate compound obtained in the step 40 with (3-aminopropyl) triethoxysilane to obtain the silane compound.

8. An antifouling paint, comprising at least one of the modified silver nanoparticles of claim 1 and the silane compound of claim 4.

9. The antifouling paint according to claim 8, wherein the mass ratio of the modified silver nanoparticles to the silane compound is 0.001-0.05: 0.5 to 5; preferably 0.004 to 0.032: 1-4.5.

10. A method for producing an antifouling paint according to any one of claims 8 to 9, comprising the steps of:

step 60, dispersing the modified nano silver particles in a liquid dispersing agent to obtain a dispersion liquid of the modified nano silver particles;

step 70, dissolving the silane compound in an organic solvent to obtain a solution of the silane compound;

and step 80, mixing and stirring the dispersion liquid of the modified nano silver particles obtained in the step 60 and the solution of the silane compound obtained in the step 70, and performing rotary evaporation to obtain a concentrated transparent liquid, namely the antifouling paint.

Technical Field

The invention relates to the field of nano materials and coating materials, in particular to the field of modified nano silver materials and antifouling coating materials.

Background

With the development of the marine industry, the problem of marine fouling of buildings, ship bodies, pipelines, oil platforms, marine sensors and the like is increasingly obvious. Marine fouling is mainly caused by marine organism pollution caused by the undesirable accumulation of marine animals, plants and microorganisms, such as barnacles, algae, fungi, shellfish and the like on the surface of underwater facilities, so that the dirt on the surface of a building is continuously accumulated to cause pipeline blockage, the sailing resistance and fuel consumption of a ship are increased, the aggravation of corrosion is promoted, and the like, and huge economic loss and serious problems are brought to the marine industry.

The most effective and convenient method of preventing marine fouling is through coatings that release toxic molecules at a controlled rate to reduce or inhibit the growth of adhering organisms such as bacteria, algae and molluscs. However, the method has the high possibility of influencing the marine environmental pollution and the growth and survival of other marine organisms, so that the development of the low-toxicity effective environment-friendly antifouling agent is extremely important.

The nano silver has low toxicity and excellent antibacterial and antifouling activity, but the release controllability of silver ions and the compatibility with the coating cannot be well controlled and improved at the present stage, so that the pollution damage to the marine environment can be caused when the nano silver is applied to the antifouling coating, and the application of the nano silver in the antifouling coating is limited.

Disclosure of Invention

In view of the problems in the background art, the present invention aims to provide a modified nano silver particle, a preparation method thereof and an antifouling paint, which can control the release controllability of silver ions, improve the compatibility of the silver particle and a coating, improve the antifouling effect of the antifouling paint, and reduce pollution and damage to the marine environment.

In order to achieve the above object, in one aspect of the present invention, the present invention provides a modified nano silver particle, which has a raspberry-like structure and includes a nano silver particle as an inner core and a tannic acid shell layer coated outside the nano silver particle, wherein nano silica particles are supported on a surface of the tannic acid shell layer.

In another aspect of the present invention, the present invention provides a method for preparing modified silver nanoparticles, which is used for preparing the modified silver nanoparticles, and comprises the following steps: step 10, reacting silver nitrate and polyvinylpyrrolidone in ethylene glycol to obtain nano silver particles; step 20, dispersing the nano silver particles obtained in the step 10 in ethanol, adding an ethanol solution of tannic acid for reaction to obtain tannic acid modified nano silver particles with a core-shell structure; and step 30, dispersing the nano silver particles with the core-shell structure modified by the tannic acid obtained in the step 20 in ethanol, adding water, and then adding an ethanol solution of ethyl orthosilicate for reaction to obtain the modified nano silver particles.

In still another aspect of the present invention, there is provided a silane compound obtained by reacting glycidyl methacrylate, hydroxyethyl methacrylate, γ -methacryloxypropyltrimethoxysilane, and (3-aminopropyl) triethoxysilane under initiation of an initiator.

In still another aspect of the present invention, there is provided a method for preparing a silane compound, comprising the steps of: step 40, reacting glycidyl methacrylate, hydroxyethyl methacrylate and gamma-methacryloxypropyl trimethoxysilane under the initiation of an initiator to obtain an intermediate compound; and step 50, reacting the intermediate compound obtained in the step 40 with (3-aminopropyl) triethoxysilane to obtain the silane compound.

In still another aspect of the present invention, the present invention provides an antifouling paint comprising at least one of the above modified silver nanoparticles and the above silane-based compound.

In still another aspect of the present invention, there is provided a method for preparing the above antifouling paint, comprising the steps of: step 60, dispersing the modified nano silver particles in a liquid dispersing agent to obtain a dispersion liquid of the modified nano silver particles; step 70, dissolving the silane compound in an organic solvent to obtain a solution of the silane compound; and step 80, mixing and stirring the dispersion liquid of the modified nano silver particles obtained in the step 60 and the solution of the silane compound obtained in the step 70, and performing rotary evaporation to obtain a concentrated transparent liquid, namely the antifouling paint.

The invention at least comprises the following beneficial effects:

in the modified nano silver particles, the nano silver particles are coated by the tannic acid to form a nano-scale core-shell structure, the tannic acid is grafted on the surfaces of the nano silver particles to modify the surfaces of the nano silver particles, so that the next step of silicon dioxide loading is facilitated, and in addition, the tannic acid has certain protein resistance and antifouling performance, and the antifouling effect of the silver particles can be further improved due to the conjugation effect; and the nano silicon dioxide particles are loaded on the surface of the tannin shell layer, so that the rate of silver ions released by the silver particles in the air or in the case of a small amount of water can be reduced. Meanwhile, the silicon dioxide is loaded on the surface of the tannin shell layer in a particle form to form a raspberry-shaped structure, and the silicon dioxide has good thermal stability and physical and chemical stability and has high specific surface area when being loaded on the surface of the tannin shell layer in a particle form, so that the synergistic effect of the nano silver particles can be increased; the finally obtained modified nano silver particles with raspberry-shaped structures can better exert the antifouling effect, reduce the occurrence of agglomeration and reduce the release speed of silver ions.

After the modified nano silver particles are coated with the nano silver particles through the tannic acid and loaded through the silicon dioxide particles, the antifouling effect is more obvious, the modified nano silver particles are suitable for an antifouling paint, can have better compatibility with the paint, and improve the antifouling performance of the antifouling paint; the modified nano silver particles have better silver ion release controllability, so that the antifouling coating containing the modified nano silver particles has the advantages of safety, low toxicity and environmental friendliness. The silane compound can form a network structure after self-crosslinking after being cured, and can improve the mechanical strength of an antifouling coating when being added into an antifouling coating; the silane compound has certain low surface energy and protein resistance, and can effectively inhibit the adsorption of microorganisms in marine environment. When the antifouling paint simultaneously comprises the modified nano silver particles and the silane compound, the modified nano silver particles and the silane compound are not simply compounded by nano particles and a coating, but are mutually connected through covalent bonds and van der Waals force, so that the antifouling paint has a better combination effect, and is particularly suitable for the severe condition requirement and the environment-friendly requirement of marine antifouling.

Drawings

FIG. 1 is a TEM transmission of each product during the preparation of example 1; wherein, (a) is a TEM transmission image of the silver nanoparticles prepared in step 10, (b) is a TEM transmission image of the tannin-modified silver nanoparticles having a core-shell structure prepared in step 20, and (c) is a TEM transmission image of the modified silver nanoparticles prepared in step 30.

FIG. 2 is a chart of UV-VIS absorption spectra of each product during the preparation of example 1;

FIG. 3 is a graph of the infrared spectra of the polymers of each product and the final product of the preparation of example 5;

FIG. 4 is a graph showing the effect of the antifouling property test on the antifouling coatings prepared in examples 10 to 15.

Detailed Description

The modified nano-silver particles of the first aspect of the invention are raspberry-like structures, and comprise nano-silver particles as an inner core and a tannic acid shell layer coated outside the nano-silver particles, wherein nano-silica particles are loaded on the surface of the tannic acid shell layer.

In the modified nano silver particles, the nano silver particles are coated by the tannic acid to form a nano-scale core-shell structure, the tannic acid is grafted on the surfaces of the nano silver particles to modify the surfaces of the nano silver particles, so that the next step of silicon dioxide loading is facilitated, and in addition, the tannic acid has certain protein resistance and antifouling performance, and the antifouling effect of the silver particles can be further improved due to the conjugation effect; and the nano silicon dioxide particles are loaded on the surface of the tannin shell layer, so that the rate of silver ions released by the silver particles in the air or in the case of a small amount of water can be reduced. Meanwhile, the silicon dioxide is loaded on the surface of the tannin shell layer in a particle form to form a raspberry-shaped structure, and the silicon dioxide has good thermal stability and physical and chemical stability and has high specific surface area when being loaded on the surface of the tannin shell layer in a particle form, so that the synergistic effect of the nano silver particles can be increased; the finally obtained modified nano silver particles with raspberry-shaped structures can better exert the antifouling effect, reduce the occurrence of agglomeration and reduce the release speed of silver ions.

In the modified silver nanoparticles according to the first aspect of the present invention, the modified silver nanoparticles are obtained by reacting silver nanoparticles with tannic acid and ethyl orthosilicate; the silver nanoparticles are prepared by reacting silver nitrate and polyvinylpyrrolidone in ethylene glycol; wherein the mass ratio of the silver nitrate to the polyvinylpyrrolidone, the glycol, the tannic acid and the ethyl orthosilicate is 0.1-2: 0.05-10: 10-500: 0.1-2: 0.005-0.20; preferably 0.5 to 2: 0.1-10: 50-250: 0.5-1.5: 0.015-0.06.

In the modified nano silver particles, the mass ratio of silver nitrate, polyvinylpyrrolidone, tannic acid and ethyl orthosilicate is reasonably controlled, so that the modified nano silver particles can be efficiently prepared, and the antifouling property of the prepared modified nano silver particles is improved.

The preparation method of the modified nano silver particles of the second aspect of the invention comprises the following steps:

step 10, reacting silver nitrate and polyvinylpyrrolidone in ethylene glycol to obtain nano silver particles;

step 20, dispersing the nano silver particles obtained in the step 10 in ethanol, adding an ethanol solution of tannic acid for reaction to obtain tannic acid modified nano silver particles with a core-shell structure;

and step 30, dispersing the nano silver particles with the core-shell structure modified by the tannic acid obtained in the step 20 in ethanol, adding water, and then adding an ethanol solution of ethyl orthosilicate for reaction to obtain the modified nano silver particles.

In the preparation method of the modified nano silver particles, silver nitrate, polyvinylpyrrolidone and glycol are added into a reaction system together for reaction; the polyvinylpyrrolidone can be used for stabilizing and dispersing the nano silver particles, so that the agglomeration phenomenon of the nano silver particles is reduced, and the further modification of the ethylene glycol can be facilitated; the glycol can be used for modifying the surface of the nano silver particles so as to facilitate the tannin grafting on the surface of the nano silver particles; the tannin is grafted on the surface of the nano silver particles, so that the antifouling effect of the nano silver particles can be improved, and preparation can be made for the next step of grafting silicon dioxide.

In the second aspect of the present invention, in the step 10, the reaction temperature of the silver nitrate and the polyvinylpyrrolidone in the ethylene glycol is 100-; preferably, in the step 10, the reaction temperature of the silver nitrate and the polyvinylpyrrolidone in the ethylene glycol is 100-150 ℃, and the reaction time is 6-24 h.

In the second aspect of the present invention, in the step 10, an organic solvent is added to a reaction product of silver nitrate and polyvinylpyrrolidone, and the modified silver nanoparticles are obtained by centrifugation and ultrasonic washing. Wherein the organic solvent is a polar solvent; preferably, the organic solvent is selected from any one of acetone or isopropanol.

In the method for preparing modified silver nanoparticles according to the second aspect of the present invention, in step 20, the reaction between the silver nanoparticles and the tannic acid is performed in a reaction system having a pH of 8 to 10, at a reaction temperature of 23 to 25 ℃ for 6 to 48 hours; preferably, in step 20, the reaction between the silver nanoparticles and the tannic acid is performed in a reaction system with a pH of 9, the reaction temperature is 23 to 25 ℃, and the reaction time is 12 to 24 hours.

In the preparation method of the modified silver nanoparticles of the second aspect of the present invention, in step 30, the reaction between the silver nanoparticles with core-shell structure modified by tannic acid and the ethyl orthosilicate is performed in a reaction system with pH of 8-10, the reaction temperature is 23-25 ℃, and the reaction time is 6-48 h; preferably, in step 30, the reaction between the tannic acid modified silver nanoparticles having a core-shell structure and the tetraethoxysilane is performed in a reaction system at a pH of 9, the reaction temperature is 23 to 25 ℃, and the reaction time is 12 to 24 hours.

The silane compound of the third aspect of the present invention is obtained by reacting glycidyl methacrylate, hydroxyethyl methacrylate, γ -methacryloxypropyltrimethoxysilane, and (3-aminopropyl) triethoxysilane under initiation of an initiator.

The silane compound of the third aspect of the present invention is named GHMK by the initials of its reactants glycidyl methacrylate GMA, hydroxyethyl methacrylate HEMA, gamma-methacryloxypropyltrimethoxysilane MPS and (3-aminopropyl) triethoxysilane KH-550.

The silane compound is synthesized by using glycidyl methacrylate, hydroxyethyl methacrylate, gamma-methacryloxypropyltrimethoxysilane and (3-aminopropyl) triethoxysilane, the cost of monomers for synthesizing products is low, and the synthesized silane compound GHMK can be self-crosslinked to form a polysilane compound PGHMK with a network structure after being cured and has higher mechanical strength.

In the silane-based compound according to the third aspect of the present invention, the molar ratio of the glycidyl methacrylate, the hydroxyethyl methacrylate, the γ -methacryloxypropyltrimethoxysilane, and the (3-aminopropyl) triethoxysilane is 1 to 9: 1-9: 1-6: 1-3; preferably 1 to 6: 1-3: 2-4: 1-2.

In the silane compound, the reaction efficiency and the reaction completeness can be improved by reasonably controlling the molar ratio of glycidyl methacrylate, hydroxyethyl methacrylate, gamma-methacryloxypropyltrimethoxysilane and (3-aminopropyl) triethoxysilane; and the silane compound prepared by the molar ratio is added into the antifouling paint, so that the antifouling paint has a good film forming effect, no bubbles are generated after film forming, the film forming thickness is moderate, and the adhesive force is good.

In the silane-based compound according to the third aspect of the invention, the initiator is azobisisobutyronitrile; the mass percentage of the azodiisobutyronitrile in the reaction system is 0.01-10 wt%; preferably, the mass ratio of the azobisisobutyronitrile in the reaction system is 0.1 to 5 wt%.

The method for preparing a silane compound of the fourth aspect of the present invention comprises the steps of:

step 40, reacting glycidyl methacrylate, hydroxyethyl methacrylate and gamma-methacryloxypropyl trimethoxysilane under the initiation of an initiator to obtain an intermediate compound;

and step 50, reacting the intermediate compound obtained in the step 40 with (3-aminopropyl) triethoxysilane to obtain the silane compound.

The preparation method of the silane compound has the advantages of simple synthesis method and low VOC in the synthesis process.

In the method for preparing silane compounds according to the fourth aspect of the present invention, the intermediate compound obtained in step 40 is named GHM by the initials of glycidyl methacrylate GMA, hydroxyethyl methacrylate HEMA, gamma-methacryloxypropyltrimethoxysilane MPS.

In the method for preparing a silane compound according to the fourth aspect of the present invention, in step 40, the reaction of glycidyl methacrylate, hydroxyethyl methacrylate and γ -methacryloxypropyltrimethoxysilane is performed in a polar organic solvent; preferably, the polar organic solvent is selected from methanol or isopropanol.

In the method for preparing a silane compound according to the fourth aspect of the present invention, in step 40, the reaction temperature of the glycidyl methacrylate, the hydroxyethyl methacrylate and the gamma-methacryloxypropyltrimethoxysilane is 60 to 120 ℃, and the reaction time is 0.5 to 12 hours; preferably, in step 40, the reaction temperature of the glycidyl methacrylate, the hydroxyethyl methacrylate and the gamma-methacryloxypropyltrimethoxysilane is 60-90 ℃ and the reaction time is 1-6 h.

In the method for preparing a silane compound according to the fourth aspect of the present invention, in step 50, the reaction temperature of the intermediate compound with (3-aminopropyl) triethoxysilane is 40-60 ℃, and the reaction time is 0.5-10 h; preferably, in step 50, the reaction temperature of the intermediate compound and (3-aminopropyl) triethoxysilane is 45-55 ℃ and the reaction time is 2-5 h.

In the method for preparing a silane compound according to the fourth aspect of the present invention, in step 50, a reaction product of an intermediate compound and (3-aminopropyl) triethoxysilane is cooled to room temperature, excess reaction liquid is spun off, a concentrated liquid obtained by the spin-evaporation is dropped into an organic solvent, and a white transparent liquid is obtained by washing a plurality of times, and the concentrated liquid is obtained by the spin-evaporation of the white transparent liquid, and the silane compound is obtained. Wherein the organic solvent is a polar solvent; preferably, the organic solvent is selected from any one of n-hexane or acetone.

The antifouling paint of the fifth aspect of the present invention includes at least one of the modified nano silver particles and the silane-based compound.

After the modified nano silver particles are coated with the nano silver particles through the tannic acid and loaded through the silicon dioxide particles, the antifouling effect is more obvious, the modified nano silver particles are suitable for an antifouling paint, can have better compatibility with the paint, and improve the antifouling performance of the antifouling paint; the modified nano silver particles have better silver ion release controllability, so that the antifouling coating containing the modified nano silver particles has the advantages of safety, low toxicity and environmental friendliness. The silane compound can form a network structure after self-crosslinking after being cured, and can improve the mechanical strength of an antifouling coating when being added into an antifouling coating; the silane compound has certain low surface energy and protein resistance, and can effectively inhibit the adsorption of microorganisms in marine environment. When the antifouling paint simultaneously comprises the modified nano silver particles and the silane compound, the modified nano silver particles and the silane compound are not simply compounded by nano particles and a coating, but are mutually connected through covalent bonds and van der Waals force, so that the antifouling paint has a better combination effect, and is particularly suitable for the severe condition requirement and the environment-friendly requirement of marine antifouling.

In the antifouling paint according to the fifth aspect of the present invention, the mass ratio of the modified silver nanoparticles to the silane-based compound is 0.001 to 0.05: 0.5 to 5; preferably 0.004 to 0.032: 1-4.5.

The method for producing an antifouling paint of the sixth aspect of the present invention comprises the steps of:

step 60, dispersing the modified nano silver particles in a liquid dispersing agent to obtain a dispersion liquid of the modified nano silver particles;

step 70, dissolving the silane compound in an organic solvent to obtain a solution of the silane compound;

and step 80, mixing and stirring the dispersion liquid of the modified nano silver particles obtained in the step 60 and the solution of the silane compound obtained in the step 70, and performing rotary evaporation to obtain a concentrated transparent liquid, namely the antifouling paint.

The preparation method of the antifouling paint is a low VOC process and has the advantage of environmental friendliness; and the prepared antifouling coating has excellent antifouling performance.

In the method of producing an antifouling paint according to the sixth aspect of the present invention, in step 60, the liquid dispersant is selected from any one of ethanol and methanol.

In the method of producing an antifouling paint according to the sixth aspect of the invention, in step 60, the modified silver nanoparticles are dispersed in the modified silver nanoparticle dispersion at a mass concentration of 0.02 mg/mL.

In the method of producing an antifouling paint according to the sixth aspect of the present invention, in step 70, the organic solvent is preferably methanol.

In the method of producing an antifouling paint according to the sixth aspect of the present invention, in step 80, the dispersion of modified silver nanoparticles and the solution of the silane compound are stirred at a temperature of 25 to 100 ℃ for 2 to 48 hours; preferably, in step 70, the dispersion of modified silver nanoparticles and the solution of the silane compound are stirred at a temperature of 30 to 60 ℃ for 2 to 24 hours.

The invention also provides an antifouling coating, which is formed by applying the antifouling coating on at least part of the surface of a substrate and then curing; preferably, the curing is carried out at a temperature of 40-150 ℃ and the duration of the curing is 12-72 h; more preferably, the curing is carried out at a temperature of 60-120 ℃ and the duration of the curing is 24-48 h.

The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.