CN111187548B - Fluorosilicone composite photocatalytic antibacterial antifouling paint and preparation method thereof - Google Patents

Abstract

The invention relates to a paint preparation technology, and aims to provide a fluorosilicone composite photocatalytic antibacterial antifouling paint and a preparation method thereof. The coating comprises the following components in percentage by mass: 20-60% of fluorosilicone acrylic resin solution, 0.1-20% of propylene glycol methyl ether acetate, 0.1-20% of nano semiconductor material with photocatalytic response, 0.1-20% of nano silicon oxide and 30-75% of organic solvent. The invention can well protect the base material while maintaining the original appearance, has high light transmittance, good scrubbing resistance and solvent resistance, and has the functions of self-cleaning and antifouling. The formed coating has excellent performances in the aspects of adhesive force, wear resistance, solvent resistance, self-cleaning and stain resistance. By introducing the photocatalytic antibacterial nano-silver filler, according to the microorganism fouling rule, fouling microorganisms are inactivated at the initial stage of microorganism fouling formation, and the long-acting self-cleaning effect is achieved under the characteristic of low surface energy of the coating.

Description

Fluorosilicone composite photocatalytic antibacterial antifouling paint and preparation method thereof

Technical Field

The invention relates to a paint preparation technology, in particular to a fluorine-silicon composite photocatalytic antibacterial antifouling paint and a preparation method thereof. The coating can be used for the antibacterial and antifouling protection of glass and other transparent or opaque inorganic nonmetal or metal surfaces, and can be used for the anticorrosion and antifouling of plastic surfaces and metal plated parts, the insulating and antifouling of wear-resistant coatings and electronic components.

Background

Glass is used as a decorative or protective surface material in many areas of life. However, the surface of the glass is rich in hydroxyl groups, belongs to a hydrophilic surface, and when the surface of the glass is in rainy days or water vapor in air encounters the surface of the supercooled glass, a water film is formed on the surface of the glass, so that the glass is easily polluted by impurities such as dust and the like. For example, the glass curtain wall is a beautiful and novel building wall decoration method, and the adhesion of dust in the air and the like on the surface of the glass curtain wall can bring about the influence of the beauty; the surface layer of the solar cell panel is mostly formed by glass, and impurities such as dust and the like are adhered to and accumulated on the surface of the solar cell panel, so that the use efficiency of the solar cell panel to sunlight is influenced; under the conditions of high salt humidity and sea wave scouring, water films formed on the surfaces of observation windows, periscopes and the like of ships and warships can influence the observation of the ships and warships on the surrounding conditions. On the other hand, under the combined action of unclean water such as seawater and microorganisms such as bacteria in the air, the surface fouling of the base materials such as glass which are difficult to clean and maintain is further aggravated.

Most antifouling self-cleaning coatings incorporate colored pigments and fillers to increase the strength of the coating, resulting in coatings that are opaque, unsuitable for antifouling self-cleaning under such conditions, and do not provide effective protection in the early stages of partial organic biofouling. The traditional method for cleaning the dirt on the surface of the glass substrate is manual treatment, the efficiency is low, scratches are possibly left on the surface of the glass, inconvenience is brought to production and life of people, and huge economic loss is caused.

The method for coating the glass surface with a coating which has high transparency, excellent wear resistance and self-cleaning and anti-fouling properties is the simplest and easiest solution to operate. In consideration of the excellent weather resistance of the acrylic resin and the simplicity of functional design of polymer resin by selecting various monomer molecules, the acrylate containing fluorine silicon is selected as a film forming substance of the wear-resistant antifouling coating.

However, the coating film obtained by polymerizing the single fluorine-containing acrylate has low surface energy, so that the coating film is easy to separate from a base material after being cured, and the hardness of the coating layer obtained by the silicon-containing acrylate does not meet the requirement. Therefore, the fluorine-containing silicon acrylic resin needs to be subjected to structure screening and proportion design so as to obtain the antifouling coating with the wear-resistant surface and the self-cleaning function.

Disclosure of Invention

The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a fluorosilicone composite photocatalytic antibacterial antifouling paint and a preparation method thereof.

The fluorosilicone composite photocatalytic antibacterial antifouling paint comprises the following components in percentage by mass: 20-60% of fluorosilicone acrylic resin solution, 0.1-20% of propylene glycol methyl ether acetate, 0.1-20% of nano semiconductor material with photocatalytic response, 0.1-20% of nano silicon oxide and 30-75% of organic solvent;

the structure of the fluorine-containing silicon acrylic resin has the following general formula (I):

in the formula, each R¹Independently selected from hydrogen or methyl; each R²Independently selected from hexafluorobutyl ester; each R³Selected from triisopropylsilyl esters, each R⁴Independently selected from methyl or isobornyl; the x group represents a fluorine-containing (methyl) acrylate monomer, the y group represents a silicon-containing (methyl) acrylate monomer, the s group represents a non-fluorine-silicon acrylate monomer, and the r group represents a reactive silane coupling agent.

According to the invention, the mass ratio of the nano silicon oxide to the nano semiconductor material with photocatalytic response is 20: 3-1: 4, and the nano silicon oxide and the nano semiconductor material with photocatalytic response jointly form the photocatalytic antibacterial nano filler.

In the present invention, the organic solvent is preferably hydrofluoroether. Alternatively, one or more of butyl acetate, ethyl acetate, acetone, methyl ethyl ketone, ethanol, tetrahydrofuran, or methanol may be selected.

In the present invention, the nano silicon oxide is preferably silicon dioxide having a particle size of 7 nm. Alternatively, silica, quartz or a combination thereof having a particle size of 1 to 1000nm may be selected.

In the invention, the nano semiconductor material with photocatalytic response is preferably one or more of nano zinc oxide, nano titanium dioxide or nano silver. Alternatively, one or a combination of two or more of nano zinc sulfide, nano cuprous oxide, nano silicon carbide, nano tin oxide, nano tungsten oxide, nano indium oxide and graphene can be selected.

The invention further provides a preparation method of the fluorosilicone composite photocatalytic antibacterial antifouling paint, which comprises the following steps:

(1) uniformly mixing 60-90 parts by weight of fluorine-containing (methyl) acrylate monomer, 10-30 parts by weight of silicon-containing (methyl) acrylate monomer, 10-40 parts by weight of acrylate monomer and 5-30 parts by weight of reactive silane coupling agent; then adding azodiisobutyronitrile as an initiator, wherein the initiator accounts for 0.2% of the total weight of all monomers; then adding hydrofluoroether with the weight equal to the total weight of all monomers, and reacting for 5-10 hours at 70 ℃ to obtain a fluorine-containing silicon acrylic resin solution;

(2) taking the following components in percentage by mass: 20-60% of fluorosilicone acrylic resin solution, 0.1-20% of propylene glycol methyl ether acetate, 0.1-20% of nano semiconductor material with photocatalytic response, 0.1-20% of nano silicon oxide and 30-75% of organic solvent; and uniformly mixing the components to obtain a fluorine-silicon composite photocatalytic antibacterial antifouling paint product.

In the invention, in the step (1):

the fluorine-containing (meth) acrylate monomer is: one or two of hexafluorobutyl methacrylate or hexafluorobutyl acrylate; alternatively, trifluoroethyl methacrylate, trifluoroethyl acrylate, hexafluorobutyl methacrylate, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate, [ N-methylperfluorooctanesulfonamido ] ethyl acrylate, [ N-methylperfluorooctanesulfonamido ] ethyl methacrylate, [ N-methylperfluorooctanesulfonamido ] ethyl acrylate, [ N-methylperfluorohexanesulfonamido ] ethyl methacrylate, [ N-methylperfluorobutanesulfonamido ] ethyl acrylate and [ N-methylperfluorobutanesulfonamido ] ethyl methacrylate, [ N-ethylperfluorooctanesulfonamido ] ethyl acrylate, [ N-ethylperfluorooctanesulfonamido ] ethyl methacrylate, [ N-ethylperfluorooctanesulfonamido ] ethyl acrylate, [ N-ethylperfluorohexanesulfonamido ] ethyl acrylate, and, One or more of [ N-ethylperfluorohexane sulfonamide ] ethyl methacrylate, [ N-ethylperfluorobutane sulfonamide ] ethyl acrylate and [ N-ethylperfluorobutane sulfonamide ] ethyl methacrylate;

the silicon-containing (meth) acrylate monomer is: one or both of triisopropylsilyl methacrylate (TISMA) or triisopropylsilyl acrylate (TISA); alternatively, tri-n-propylsilyl methacrylate, tri-n-propylsilyl acrylate, triisopropylsilyl methacrylate, triisopropylsilyl acrylate, tri-n-butylsilyl methacrylate, tri-n-butylsilyl acrylate, triisobutylsilyl methacrylate, triisobutylsilyl acrylate, t-butyldimethylsilyl methacrylate, t-butyldimethylsilyl acrylate, t-hexyldimethylsilyl methacrylate, t-hexyldimethylsilyl acrylate, t-butyldiphenylsilyl methacrylate, t-butyldiphenylsilyl acrylate, nonamethyltetrasiloxyalkyl methacrylate, nonamethyltetrasiloxyalkyl acrylate, bis (trimethylsiloxy) silyl methacrylate, tris (isopropylsilyl) acrylate, triisobutylsilyl acrylate, tert-butyldimethylsilyl methacrylate, and mixtures thereof, One or more of bis (trimethylsiloxy) methylsilyl acrylate, tris (trimethylsiloxy) silyl methacrylate or tris (trimethylsiloxy) silyl acrylate;

the acrylate monomers are: one or more of methyl methacrylate, methyl acrylate, isobornyl methacrylate or isobornyl acrylate; alternatively, one or more of ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, isooctyl acrylate, isooctyl methacrylate, stearyl acrylate, stearyl methacrylate and the like can be selected;

the reactive silane coupling agent is gamma-methacryloxypropyltrimethoxysilane KH-570.

The invention also provides a use method of the fluorine-silicon composite photocatalytic antibacterial antifouling paint, which comprises the following steps:

(1) cleaning the surface of a substrate to be coated;

(2) uniformly coating the fluorine-silicon composite photocatalytic bacteriostatic antifouling coating on the surface of a base material, wherein the coating thickness is 10-180 mu m; and drying for 8-24 hours in a ventilated and dry room temperature environment to enable the fluorosilicone composite photocatalytic antibacterial antifouling paint layer to be tightly adhered to the surface of the substrate.

In the present invention, "alkyl" is intended to cover both straight-chain or branched alkyl groups, such as methyl, ethyl, isopropyl, propyl, butyl, and tert-butyl. Cycloalkyl includes cyclohexyl and substituted cyclohexyl.

Description of the inventive principles:

the initial stage of fouling on the solid surface is a stage of forming a basement membrane (conditioning film), wherein a layer of organic matter mainly composed of protein, polysaccharide and the like is adsorbed on the surface to form the basement membrane, which is also called as a conditioned membrane; then, microorganisms such as bacteria, diatom and the like attach to the basement membrane and secrete extracellular metabolites (EPS) to form a biofilm (biofilm) or a mucosa (slime) in a short time; other prokaryotes, fungi, algal spores, and larval fouling organisms then develop and grow in the membrane, eventually forming a complex layer of large fouling organisms (macrolayers).

In order to effectively kill and control bacteria, fungi and other microorganisms at the initial stage of biofouling formed on the solid surface, the invention introduces the nano-filler with photocatalysis and bacteriostasis to maintain the long-acting self-cleaning function of the coating under the action of the low surface energy characteristic of the fluorine-silicon composite coating. The titanium dioxide and the copper element or the zinc element in the semiconductor material can be used as coordination centers to form coordination bonds with silicate ions, the nano cuprous oxide and the nano zinc oxide are used as reaction centers, the titanium dioxide, the silicon oxide and the resin are used as carriers, and the nano cuprous oxide and the nano zinc oxide particles are dispersed. The formed nano siloxy copper oxide/zinc has high reactivity, can activate oxygen in air or water under the condition of illumination to generate hydroxyl free radicals and active oxygen ions, and inactivates microorganisms under the condition of illumination.

The nano semiconductor material with photocatalytic and bacteriostatic response comprises nano zinc sulfide, nano zinc oxide, nano cuprous oxide, nano silicon carbide, nano titanium dioxide, nano tin oxide, nano tungsten oxide, nano indium oxide, graphene, nano silver powder and the like, and the sterilization and inactivation principle of the nano semiconductor material is related to the photocatalytic property and the energy band structure of the semiconductor material. The electronic band structure of the semiconductor material is discontinuous and comprises a valence band, a conduction band and a forbidden band, wherein the forbidden band is a wider interval between the valence band and the conduction band, an energy difference exists between the highest energy level (valence band top) of the valence band and the lowest energy level (conduction band bottom) of the conduction band, when the semiconductor material is irradiated by light with photon energy larger than or equal to the width of the semiconductor forbidden band, electrons in the valence band of the semiconductor are excited by light and jump to the conduction band, electrons are formed in the conduction band, holes are left in the valence band at the same time, and photo-generated electron-hole pairs are formed, one part of the photo-generated electron-hole pairs can be recombined in the semiconductor, and the other part of the photo-generated electron-hole pairs can be separated under the action of an electric field and can migrate to different positions on the surface of the semiconductor. On one hand, the photo-generated electrons and photo-generated holes generated in the photocatalysis process can directly attack microbial cells, so that bioactive proteins and the like of the microbial cells are damaged and lose activity. On the other hand, the cavity can react with water and hydroxyl ions adsorbed on the surface of the semiconductor material to generate hydroxyl radicals and hydrogen peroxide; the electrons react with the adsorbed oxygen on the surface of the coating to generate superoxide radicals, further generate hydroxyl radicals, hydrogen peroxide and the like. The active oxygen substance has strong oxidizing property, and can oxidize and decompose various organic substances into inorganic substances such as water, carbon dioxide, carbonate and the like, thereby killing microorganisms such as bacteria and the like.

The invention overcomes the defects of poor adhesive force and poor abrasion resistance of the prior fluorine-silicon low-surface-energy antifouling coating and the surfaces of glass and other base materials; the coating has the characteristics of high apparent transparency while improving the strength; the coating has the functions of photocatalysis and bacteriostasis, and effectively prevents the surface from being polluted by organisms. In terms of construction application, the defect that the fluorine-containing silicon acrylic resin system cannot be popularized due to overhigh preparation cost is overcome, and the problem that the surface transparency effect and the decoration effect of the base material are reduced due to poor compatibility of a common antifouling self-cleaning coating system for transparent coating of the base material such as glass is solved.

Compared with the prior art, the invention has the beneficial effects that:

1. the invention can be applied to the technical field of solvent-based coatings and used for surface protection treatment of substrates, and the fluorosilicone composite photocatalytic antibacterial antifouling coating can be widely applied to antibacterial antifouling protection of various glass and other transparent or opaque inorganic nonmetal or metal surfaces and is used for corrosion prevention and antifouling of plastic surfaces and metal plated parts, so that the substrates are well protected while the original appearance of the substrates is maintained, and the coating has high light transmittance, good scrubbing resistance and solvent resistance, and has self-cleaning antifouling functions.

2. The fluorine-containing acrylic monomer providing low surface energy of the coating is combined with the silicon-containing acrylic monomer, the (methyl) acrylic ester and the reactive silane coupling agent gamma-methacryloxypropyltrimethoxysilane KH-570 are added, and the respective physical properties of the four monomers and the surface performance after film forming are integrated, so that the formed coating has excellent performances in the aspects of adhesive force, wear resistance, solvent resistance, self-cleaning and anti-fouling.

3. By introducing the photocatalytic antibacterial nanofiller (nano-silver), according to the microorganism fouling rule, fouling microorganisms are inactivated at the initial stage of microorganism fouling formation, and the long-acting self-cleaning effect is achieved under the characteristic of low surface energy of the coating.

Detailed Description

The present invention will be described in further detail with reference to specific examples and comparative examples. The examples may provide those skilled in the art with a more complete understanding of the present invention, and are not intended to limit the invention in any way.

A fluorine-silicon composite photocatalytic bacteriostatic antifouling coating and a preparation method thereof comprise the following steps:

the method comprises the following steps:

uniformly mixing 60-90 parts by weight of fluorine-containing (methyl) acrylate monomer, 10-30 parts by weight of silicon-containing (methyl) acrylate monomer, 10-40 parts by weight of acrylate monomer and 5-30 parts by weight of reactive silane coupling agent; then adding azodiisobutyronitrile as an initiator, wherein the initiator accounts for 0.2% of the total weight of all monomers; then adding hydrofluoroether with the weight equal to the total weight of all monomers, and reacting for 5-10 hours at 70 ℃ to obtain a fluorine-containing silicon acrylic resin solution;

step two:

taking the following components in percentage by mass: 20-60% of fluorosilicone acrylic resin solution, 0.1-20% of propylene glycol methyl ether acetate, 0.1-20% of nano semiconductor material with photocatalytic response, 0.1-20% of nano silicon oxide and 30-75% of organic solvent; and uniformly mixing the components to obtain a fluorine-silicon composite photocatalytic antibacterial antifouling paint product.

Step three: coating of the coating:

cleaning the surface of a substrate to be coated; uniformly coating the fluorine-silicon composite photocatalytic antibacterial antifouling paint on the surface of a base material in an air spraying manner, wherein the coating thickness is 10-180 mu m (wet film); and drying for 8-24 hours in a ventilated and dry room temperature environment to enable the fluorosilicone composite photocatalytic antibacterial antifouling paint layer to be tightly adhered to the surface of the substrate.

After the fluorosilicone composite photocatalytic antibacterial antifouling coating prepared by the method is cured on glass, the pencil hardness can reach 6H to the maximum, and the adhesive force is grade 1.

The preparation method of the fluorosilicone composite photocatalytic bacteriostatic antifouling coating is shown in the following 5 examples, and the test data of each example is shown in table 1 below.

Table 1 data table of examples

Verification of technical effects

The coating obtained from the fluorosilicone composite abrasion-resistant antifouling paint composition prepared as described above was subjected to a tape peeling test, a pencil hardness test, an ethanol wiping resistance test, a brine resistance test, and a self-cleaning test in the following procedures. These results are shown in Table 2.

TABLE 2 proportioning composition of fluorosilicon composite photocatalytic antibacterial antifouling coating and test results

	Example 1	Example 2	Example 3	Example 4	Example 5
						Cross cut tape peel test	Class I	Class I	Class I	Class I	Class I
Pencil hardness test	5H	5H	5H	6H	6H
						Accelerated wear test	Class I	Class I	Class I	Class I	Class I
Ethanol rub resistance test	Class I	Class I	Class I	Stage II	Stage II
						Experiment for salt Water tolerance	Is flat and smooth	Is flat and smooth	Is flat and smooth	Is flat and smooth	Is flat and smooth
Self-cleaning test	Is excellent in	Good effect	Good effect	Good effect	Good effect
						Shallow sea bacteriostatic antifouling test	Stage II	Class I	Stage II	Class I	Stage II

The test method for each validation experiment is illustrated below:

(test for peeling tape)

Coating adhesion refers to the ability of the paint film to bond to the surface of the substrate being coated or to the coating. The adhesive force is an important technical index and is a precondition that a paint film has a series of performances. The coating combines well, and is not fragile, drops, just can play good antifouling and guard action to the substrate when resistant external wear.

The 25mm × 75mm × 1mm glass slide was thoroughly washed with ethanol, and after completely drying, the fluorosilicone composite photocatalytic antibacterial antifouling coating prepared in examples 1 to 10 and comparative examples 1 to 4 was applied at normal temperature using a spray pen, and was dried for 24 hours.

And drawing a lattice pattern with the interval of 1mm multiplied by 1mm on the coating sample plate by using a multi-edge cutter, wherein 6 or 11 scratches are formed on each edge, and then brushing off chips by using a brush. In this operation, the multi-edge tool scratches should be made to penetrate the coating film. The adhesive tape is immediately stuck on the scratch of the coating film, and is flatly pressed and firmly pressed by a pen-head eraser or a fine cloth. And (5) rapidly tearing the adhesive tape from the coating film, and observing the damage condition of the scratch and the coating film by using a magnifying lens. The adhesion was rated as follows.

Stage I: the coating film does not fall off completely

And II, stage: the film falling is not more than 10 percent

Grade III: the film falling is not more than 25 percent

IV stage: the film falling is not more than 50 percent

And V stage: film coating falling off more than 50%

(Pencil hardness test)

The pen tip was first ground vertically flat on fine sandpaper (1000#) and mounted on a hardness tester. The inclination is about 25 mm. And (3) placing weights on the hardness tester, shaking the machine to do uniform motion, and visually observing whether the surface of the paint film is scratched or not. The Chinese pencil can be replaced according to the condition that the paint film is scratched or not. Or judging the hardness under the condition of adding weights.

(accelerated wear test)

Cutting fine sand paper (1000#) into 2cm × 2cm, adhering the fine sand paper to the bottom of a 250g weight by using a double-sided adhesive tape, rubbing the surface of the measured coating at a speed of 5cm/s, and observing the surface of the paint film whether chips exist or not after a certain reciprocating period. Judging the accelerated wear test effect according to the situation that the chipping occurs on the surface of the paint film.

Stage I: the coating film is not obviously damaged after 100 reciprocating

And II, stage: chipping occurred on 80 reciprocating rear surfaces of the coating film

Grade III: chipping of the coating film occurred on the 60-cycle rear surface

IV stage: chipping occurred on the coating film at 40 reciprocating rear surfaces

And V stage: chipping of the coating film occurred on the 20 reciprocating rear surfaces

(ethanol resistance wiping test)

The coating sample plate is fixed on a table, absorbent cotton which is completely wetted by ethanol is placed on the coating sample plate, a weight of 250g is placed on the absorbent cotton to serve as a load, repeated friction is carried out, and after a certain reciprocating period, whether chips exist on the surface of the paint film is visually observed. Judging the ethanol wiping resistance effect according to the chipping condition of the surface of the paint film.

Stage I: the coating film is not obviously damaged after 200 reciprocating

And II, stage: chipping occurred on 150 reciprocating rear surfaces of the coating film

Grade III: chipping of the coating film occurred on 100 reciprocating rear surfaces

IV stage: chipping of the coating film occurred on the 50 reciprocating rear surfaces

And V stage: chipping of the coating film occurred on the 20 reciprocating rear surfaces

(salt Water resistance test)

The salt water resistance of the coating is one of the basic weather resistance of the paint film. When the coating is coated on a base material used in special environments such as building glass outer walls, observation windows of maritime work equipment, marine ships and the like, the coating can be subjected to acid rain corrosion, high salt humidity and other complex environments. Whether the coating can play a basic protection role on the substrate in a sodium chloride solution with a certain concentration can be judged through a salt water resistance test.

And soaking the sample plate in artificial seawater at 23 ℃ for 1000 hours, and evaluating the surface appearance of a paint film of the sample plate.

(self-cleaning test)

Paste prepared from nano titanium dioxide and hexadecane is uniformly paved on the surface of the sample plate, water drops are dripped on the surface of a polluted sample, the inclination angle is 20 degrees, and the self-cleaning performance of the coating under the rainwater scouring condition under the natural condition is simulated.

Excellent: the coating surface is self-cleaning

Excellent: little fouling on the surface of the coating film

In general: obvious fouling on the surface of the coating film

(shallow sea bacteriostasis antifouling test)

And testing the antibacterial and antifouling performance of the coating. The test method is carried out according to the national standard GB/T5370-2007 shallow sea immersion test method for antifouling paint sample plates. The base material is a low-carbon steel plate with the thickness of 3mm and the size of 350mm multiplied by 250mm, and the epoxy anti-corrosion primer is coated in advance. The shallow sea soaking period is 1 month.

Stage I: extremely thin mucus was observed, but the adhesion of animal species was not observed

And II, stage: adhesion of mucus was confirmed, but adhesion of animal species was not confirmed

Grade III: thick mucus was observed, but animal species were not observed

IV stage: confirming fouling of animal species

And V stage: the adhesion of animal species was confirmed throughout the coating film

While the invention has been described in detail herein and illustrated in the examples section by way of examples, various modifications and alternatives can be made. It should be understood, however, that there is no intention to limit the invention to the specific forms disclosed. Rather, the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the following appended claims.

Claims (8)

1. A fluorine-silicon composite photocatalytic bacteriostatic antifouling paint is characterized in that the paint comprises the following components in percentage by mass: 20-60% of fluorosilicone acrylic resin solution, 0.1-20% of propylene glycol methyl ether acetate, 0.1-20% of nano semiconductor material with photocatalytic response, 0.1-20% of nano silicon oxide and 30-75% of organic solvent;

the structure of the fluorine-containing silicon acrylic resin has the following general formula (I):

formula (I)

In the formula, each R¹Independently selected from hydrogen or methyl; each R²Independently selected from hexafluorobutyl ester; each R³Selected from triisopropylsilyl esters, each R⁴Independently selected from methyl or isobornyl; x group represents fluorine-containing (methyl) acrylate monomer, y group represents silicon-containing (methyl) acrylate monomer, s group represents non-fluorine-silicon acrylate monomer, and r group represents reactive silane coupling agent;

the fluorine-containing silicon acrylic resin solution is prepared by the following steps: uniformly mixing 60-90 parts by weight of fluorine-containing (methyl) acrylate monomer, 10-30 parts by weight of silicon-containing (methyl) acrylate monomer, 10-40 parts by weight of acrylate monomer and 5-30 parts by weight of reactive silane coupling agent; then adding azodiisobutyronitrile as an initiator, wherein the initiator accounts for 0.2% of the total weight of all monomers; then adding hydrofluoroether with the same weight as the total weight of all the monomers, and reacting for 5-10 hours at 70 ℃ to obtain the fluorine-containing silicon acrylic resin solution.

2. The fluorosilicone composite photocatalytic antibacterial antifouling paint as claimed in claim 1, wherein the mass ratio of the nano silicon oxide to the nano semiconductor material with photocatalytic response is 20: 3-1: 4, and the nano silicon oxide and the nano semiconductor material jointly form a photocatalytic antibacterial nano filler.

3. The fluorosilicone composite photocatalytic antibacterial antifouling paint as claimed in claim 1, wherein the organic solvent is hydrofluoroether.

4. The fluorosilicone composite photocatalytic antibacterial antifouling paint as claimed in claim 1, wherein the nano silicon oxide is silicon dioxide with a particle size of 7 nm.

5. The fluorosilicon composite photocatalytic antibacterial antifouling paint as claimed in claim 1, wherein the nano semiconductor material with photocatalytic response is one or more of nano zinc oxide, nano titanium dioxide or nano silver.

6. The fluorosilicon composite photocatalytic antibacterial antifouling paint as claimed in claim 1, wherein the fluorine-containing (meth) acrylate monomer is: one or two of hexafluorobutyl methacrylate or hexafluorobutyl acrylate; the silicon-containing (meth) acrylate monomer is: one or two of triisopropylsilyl methacrylate or triisopropylsilyl acrylate; the acrylate monomers are: one or more of methyl methacrylate, methyl acrylate, isobornyl methacrylate or isobornyl acrylate; the reactive silane coupling agent is gamma-methacryloxypropyltrimethoxysilane KH-570.

7. The preparation method of the fluorosilicon composite photocatalytic antibacterial antifouling paint as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:

taking the following components in percentage by mass: 20-60% of fluorosilicone acrylic resin solution, 0.1-20% of propylene glycol methyl ether acetate, 0.1-20% of nano semiconductor material with photocatalytic response, 0.1-20% of nano silicon oxide and 30-75% of organic solvent; and uniformly mixing the components to obtain a fluorine-silicon composite photocatalytic antibacterial antifouling paint product.

8. The use method of the fluorosilicon composite photocatalytic antibacterial antifouling paint disclosed by claim 1 is characterized by comprising the following steps of:

(1) cleaning the surface of a substrate to be coated;

(2) uniformly coating the fluorine-silicon composite photocatalytic bacteriostatic antifouling coating on the surface of a base material, wherein the coating thickness is 10-180 mu m; and drying for 8-24 hours in a ventilated and dry room temperature environment to enable the fluorosilicone composite photocatalytic antibacterial antifouling paint layer to be tightly adhered to the surface of the substrate.