CN117143518B

CN117143518B - Coating composition and preparation method and application thereof

Info

Publication number: CN117143518B
Application number: CN202311009142.XA
Authority: CN
Inventors: 林永权; 邓肖锋; 刘晓丽; 白晶莹; 刘广明; 文陈; 赵有强; 舒文祥; 张有玮; 张立功; 崔庆新; 张家强
Original assignee: Beijing Satellite Manufacturing Factory Co Ltd; China Resources Cement Technology R&D Co Ltd
Current assignee: Beijing Satellite Manufacturing Factory Co Ltd; China Resources Cement Technology R&D Co Ltd
Priority date: 2023-08-10
Filing date: 2023-08-10
Publication date: 2025-03-14
Anticipated expiration: 2043-08-10
Also published as: CN117143518A

Abstract

The invention provides a coating composition, a preparation method and application thereof. The coating composition disclosed by the invention is prepared from the following raw materials of a PMOS precursor, a structure directing agent, a ceramic precursor, alkoxy silane and fluorosilane, wherein the functionality of the alkoxy silane is more than or equal to 2. When the coating composition is applied to the surface of the cement-based inorganic artificial stone, a coating with good transparency, wear resistance and antifouling effect can be formed. The invention also provides a method for preparing the coating composition, an antifouling coating and application of the antifouling coating on the surface of the cement-based inorganic artificial stone.

Description

Coating composition and preparation method and application thereof

Technical Field

The invention belongs to the technical field of coatings, and particularly relates to a coating composition, a preparation method and application thereof.

Background

The cement-based inorganic artificial stone is increasingly widely applied in the field of building materials, the surface of the artificial stone decorative material has certain porosity and surface roughness, and the artificial stone decorative material cannot be stained and corroded by various pollution liquids in daily use, wherein the artificial stone decorative material comprises common liquids such as soy sauce, milk, cola, concentrated tea, red wine and the like, and also comprises various acidic liquids such as table vinegar, citric acid and the like which have corrosion hazard on alkaline plates. These contaminants are susceptible to physical adsorption by the pores in the material and also react with free hydroxyl groups on the substrate surface to form chemisorption or corrosion. These stains are easily accumulated and difficult to remove, affecting aesthetics and service life. Meanwhile, the cement-based inorganic artificial stone floor and other application scenes require that the protective coating has high transparency, so that defects such as scratches and the like are avoided as much as possible in long-term use, and a good appearance state and a long service life are maintained.

At present, the cement-based inorganic artificial stone antifouling mainly adopts a permeable protective agent and a coating protective agent. Some research and development personnel put forward a cleaning method of the inorganic artificial stone, and the antifouling property of the inorganic artificial stone is improved by adopting fine polishing and cleaning agent treatment. Some research and development personnel develop a permeable film-forming stone protective agent of modified nano titanium dioxide hydrosol, and the permeable film-forming stone protective agent has a higher contact angle and an excellent oil stain prevention effect. The permeability protective agents effectively improve the pollution problem of the cement-based inorganic artificial stone, but the traditional permeability protective agents have limited improvement of the pollution resistance of the cement-based inorganic artificial stone, have short effect duration and have no outstanding pollution resistance and corrosion resistance. The treatment of impervious sealing agents such as crystallization paste, glaze sealing agent and the like requires periodic maintenance, and the cost of labor time is high. The partially crystallized paste and the glaze sealing agent even react with acidic substances to be corroded, so that the protective layer is damaged.

In addition, the coating type protective agent with the film-formed surface has better antifouling and anti-corrosion effects, and the protective coating has higher antifouling and anti-corrosion properties, so that the requirements of antifouling and anti-corrosion of the cement-based inorganic artificial stone can be met. However, the hardness of the coating is insufficient, the pencil hardness is lower than 6H, and a large number of scratches are easily generated in the use process of the cement-based inorganic artificial stone floor, so that the appearance of the base material is influenced and the service life of the base material is prolonged. Therefore, there is still a need to develop a new coating composition which can form a transparent, abrasion-resistant, anti-fouling coating when applied to the surface of cement-based inorganic artificial stone.

Disclosure of Invention

The present invention aims to solve at least one of the above technical problems in the prior art. Therefore, the invention provides a coating composition which can form a coating with good transparency, wear resistance and antifouling effect when being applied to the surface of cement-based inorganic artificial stone.

The invention also provides a method of preparing the coating composition.

The invention also provides an antifouling coating.

The invention also provides a method for preparing the antifouling coating.

The invention also provides application of the antifouling coating on the surface of the cement-based inorganic artificial stone.

The invention provides a coating composition, which is prepared from a PMOS precursor, a structure directing agent, a ceramic precursor, alkoxysilane and fluorosilane, wherein the functionality of the alkoxysilane is more than or equal to 2, and the PMOS precursor has a structure shown as a formula (I) or a formula (II):

Wherein, R ₁ and R ₂ are independently selected from at least one of alkane, alkene and amine, and R ₃ is selected from methyl or ethyl.

The invention relates to one of the technical schemes of a coating composition, which has at least the following beneficial effects:

The coating composition of the invention adopts PMOS precursors with special structures, and can form a skeleton structure with periodic arrangement through self-polymerization of a structure directing agent. Free active sites remain in the periodic framework, potentially reacting with stains, chemicals. The network skeleton formed by the alkoxy silane with the functionality degree more than or equal to 2 and the ceramic precursor and the free active points are subjected to free radical polymerization reaction, so that inorganic ceramic chemical bonds are inserted into the periodic skeleton formed by the PMOS precursor, the mechanical strength and the stability of the coating structure are enhanced, and the formed coating has the characteristics of high hardness and high wear resistance and has higher scratch resistance.

According to the coating composition, a large number of groups such as silicon-oxygen bonds and fluorine-containing groups are connected into the active points of the periodic framework, and various functional groups are orderly arranged in the framework by utilizing the periodic arrangement mode of the framework, so that free active points are reduced. Meanwhile, the orderly arranged fluorine-containing groups in the fluorosilane can reduce the surface energy of the coating, so that the adsorption of pollutants and the corrosion of chemicals can be reduced, and the coating formed by the coating composition has excellent antifouling property and corrosion resistance.

The coating composition of the invention has the advantages that the active points in the framework and the groups and ions of the coupling agent on the surfaces of the organic and inorganic substrates have physical and chemical effects, so that the coating composition can be firmly combined with the surfaces of the substrates, and has higher binding force.

The coating composition of the invention, after drying, forms an antifouling coating which is transparent, abrasion-resistant and antifouling. The pencil hardness of the coating can reach 9H, the friction time of 1kg of steel wool is more than 4000 times, the stain is stained for not less than 24 hours, and the color difference delta E of the coating is less than or equal to 1.5. Tolerable stains include, but are not limited to, caustic stains (including but not limited to table vinegar, cola), dye-based stains (including but not limited to dark tea, ink), grease-based stains (including but not limited to animal oils, vegetable oils). The visible light transmittance is more than or equal to 95 percent, and the coating is not damaged and yellow after 1000h of xenon lamp aging acceleration time, and the color difference delta E is less than or equal to 1. The chemical resistance is better than that of C4 grade. After the coating is coated on the surface of the artificial stone, the waterproof performance of the artificial stone is more than or equal to 95 percent. The bonding force cross-hatch method level is better than level 1.

The coating composition provided by the invention has better antifouling and anti-corrosion effects and longer duration of effects compared with an artificial stone permeability protective agent. Compared with the common protective coating, the coating has good transparency, higher hardness and wear resistance, and can be used on the ground for a long time.

In the coating composition of the present invention, the PMOS precursor may be either self-made or commercially available. The structure of the precursor accords with the structure of the PMOS precursor defined by the invention. Based on the structure of the PMOS precursor defined by the invention, under the induction of the structure directing agent, the self-polymerization reaction forms a silica skeleton with periodical arrangement sequence, and the mechanical strength and the stability are superior to those of other silica structures.

According to the coating composition disclosed by the invention, the solvent system meets the environmental protection requirement, and the coating is nontoxic and odorless after being completely cured.

According to some embodiments of the invention, the PMOS precursor has a molecular weight of 10000 or less.

According to some embodiments of the invention, the preparation raw materials comprise, in parts by weight:

100 parts of PMOS precursor, namely,

0.1 To 0.5 part of structure guiding agent,

50-90 Parts of ceramic precursor,

50-200 Parts of alkoxy silane,

10-20 Parts of fluorosilane.

According to some embodiments of the invention, the structure directing agent comprises at least one of a triblock copolymer, cetyltrimethylammonium bromide, cetyltrimethylpyridinium bromide, and alkyltrimethylammonium chloride.

The dosage of the structure directing agent and the dropping speed of the solution are in a certain range, so that the periodic arrangement framework has larger defects caused by excessive side reactions.

According to some embodiments of the invention, the structure directing agent comprises P123.

According to some embodiments of the invention, the ceramic precursor comprises at least one of zirconium n-propoxide, ethyl orthosilicate, and butyl n-titanate.

A plurality of connected silica bonds are inserted into the periodically arranged frameworks, so that the coating framework structure is more stable and the performance is better. Fluorine-containing branched chains are arranged on branches in the framework to form fluorine-containing groups with periodic structures, so that the coating has better hydrophobicity.

According to some embodiments of the invention, the alkoxysilane comprises at least two of methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, 3- [ (2, 3) -glycidoxy ] propylmethyldimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, and dimethyldiethoxysilane.

According to some embodiments of the invention, the fluorosilane comprises at least one of dodecafluoroheptyl propyl trimethoxysilane, perfluorooctyl trimethoxysilane, tridecafluorooctyl triethoxysilane, and heptadecafluorodecyl trimethoxysilane.

According to some embodiments of the invention, when the PMOS precursor is 100 parts by weight, the preparation raw material further includes:

300-500 parts of organic solvent

10 To 15 parts of catalyst,

30-50 Parts of water.

According to some embodiments of the invention, the organic solvent comprises at least one from among methanol, ethanol, n-propanol and n-butanol.

According to some embodiments of the invention, the organic solvent is used in an amount of about 1 to 3 times the total amount of the remaining reagents.

According to some embodiments of the invention, the catalyst comprises at least one of an inorganic base, an alkali metal hydroxide, or a metal carboxylate.

In a second aspect, the present invention provides a method of preparing the coating composition comprising the steps of:

preparing polysiloxane solution by using the structure directing agent, the PMOS precursor, part of the organic solvent, the catalyst and water;

preparing fluorine modified silica sol by using the ceramic precursor, alkoxy silane, fluorosilane, part of the organic solvent, catalyst and water;

And (3) uniformly mixing the polysiloxane solution and part of the organic solvent, adding the fluorine modified silica sol, and refluxing to obtain the coating composition.

The invention relates to a technical scheme in a preparation method of a coating composition, which has at least the following beneficial effects:

the preparation method of the coating composition does not need expensive equipment and complicated process control, has low reaction conditions, easily obtained raw materials, low production cost and easy industrial production.

According to some embodiments of the present invention, in addition to PMOS precursors, structure directing agents, ceramic precursors, alkoxysilanes, fluorosilanes, organic solvents, catalysts, and water, other adjuvants, such as thixotropic agents and wetting agents, may be added to the coating composition according to specific requirements, such as the specific conditions of the construction process and the type of substrate.

One of the functions of the thixotropic agent is to ensure that the coating is able to adapt to different construction processes and to prevent the solid fillers possibly added from settling.

One of the functions of the wetting agent is to ensure that the coating has good wetting effect on a substrate with nonuniform surface energy and can be quickly leveled.

According to some embodiments of the invention, the thixotropic agent includes a polyurea-type thixotropic agent and a modified polyurea-type thixotropic agent.

According to some embodiments of the invention, the wetting agent comprises a silicone-based wetting agent.

According to some embodiments of the present invention, during the preparation method of the coating composition, a "part of the organic solvent" may be added as appropriate, generally in an amount of 1 to 3 times the total amount of the remaining reagents in the step.

According to some embodiments of the invention, the polysiloxane solution is prepared by:

A1, uniformly mixing the structure directing agent and part of the organic solvent, uniformly mixing part of the catalyst and water, adding the mixed solution of the catalyst and water into the mixed solution of the structure directing agent and the solvent in a stirring state, adjusting the pH value, and refluxing for 1-1.5 h at 100-120 ℃;

A2, cooling the solution prepared in the step A1 to 60-80 ℃, mixing part of the organic solvent with the PMOS precursor, adding the mixture into the cooled solution prepared in the step A1, and refluxing for 2-3 hours;

A3, stopping heating, cooling to room temperature under the stirring condition, and performing silica gel column chromatography separation to obtain the polysiloxane solution.

According to some embodiments of the invention, the polysiloxane solution may be prepared by:

After uniformly mixing part of the organic solvent and the structure directing agent, introducing the mixture into a three-neck flask, and keeping stirring at 1500-2000 rpm;

After uniformly mixing the catalyst and deionized water, slowly dripping a mixed solution of the catalyst and the deionized water into a three-neck flask under a stirring state, adjusting the pH of the solution to 9-10 at the dripping speed of 2-3 mL/min, and continuously refluxing for 1-1.5 h at 100-120 ℃;

the temperature of the solution is reduced to 60-80 ℃, part of the organic solvent and the PMOS precursor are mixed and then added into a three-neck flask, the dropping speed is 2-3 mL/min, and then the reflux is continued for 2-3 h;

Stopping heating, maintaining magnetic stirring, and performing silica gel column chromatography separation after the three-neck flask is air cooled to room temperature to obtain polysiloxane solution with a periodic framework structure.

According to some embodiments of the invention, the mobile phase can be selected from petroleum ether/ethyl acetate system by silica gel column chromatography separation, and the volume ratio is about 50-90:1. The silica gel is 100-200 mesh silica gel.

According to some embodiments of the invention, the preparation method of the fluorine modified silica sol comprises the following steps:

B1, uniformly mixing the ceramic precursor, the alkoxy silane and part of the organic solvent;

b2, uniformly mixing part of the catalyst and water, adding the mixed solution of the catalyst and the water into the mixed solution prepared in the step B1 in a stirring state, adjusting the pH value, and refluxing for 1-1.5 h at 60-80 ℃;

And B3, adding the fluorosilane into the mixed solution prepared in the step B2, and continuously refluxing for 1-1.5 h to obtain the fluorine modified silica sol.

According to some embodiments of the invention, the preparation method of the fluorine modified silica sol may be:

Uniformly mixing part of the organic solvent, the ceramic precursor and the alkoxy silane, and placing the mixture into a three-neck flask, and magnetically stirring at 1500-2000 rpm;

After the mixture is completely and uniformly stirred, slowly dripping a mixed solution of a catalyst and deionized water into a three-neck flask under a stirring state, adjusting the pH of the solution to 9-10 at the dripping speed of 2-3 mL/min, and refluxing for 1-1.5 h at 60-80 ℃;

And then dripping the fluorosilane mixture into a three-neck flask at a dripping speed of 2-4 mL/s, and keeping the temperature for continuous reflux for 1.5-2 h to obtain the fluorine modified silica sol.

According to some embodiments of the present invention, in the preparation method of the coating composition, after the polysiloxane solution and a part of the organic solvent are mixed uniformly, the fluorine modified silica sol is added, and the coating composition is obtained after reflow, the specific method may be:

Uniformly mixing part of the organic solvent and the polysiloxane solution, and placing the mixture into a three-neck flask, and keeping magnetic stirring at 1500-2000 rpm;

Then dripping fluorine modified silica sol into the three-neck flask, wherein the dripping speed is 2-4 mL/s, and refluxing is carried out for 1.5-2 h at 60-80 ℃;

and finally, filtering the prepared solution through a 200-mesh copper mesh to obtain the coating composition.

In a third aspect the invention provides an antifouling coating obtainable by curing said coating composition.

The invention relates to one of the technical schemes of an antifouling coating, which has at least the following beneficial effects:

The antifouling coating layer of the present invention is obtained by curing the coating composition of the present invention, and thus has at least all the advantageous effects of the coating composition. Specifically:

the antifouling coating adopts PMOS precursor with special structure, and can form skeleton structure with periodic arrangement through self-polymerization of structure directing agent. Free active sites remain in the periodic framework, potentially reacting with stains, chemicals. The network skeleton formed by the alkoxy silane with the functionality degree more than or equal to 2 and the ceramic precursor and the free active points are subjected to free radical polymerization reaction, so that inorganic ceramic chemical bonds are inserted into the periodic skeleton formed by the PMOS precursor, the mechanical strength and the stability of the coating structure are enhanced, and the formed coating has the characteristics of high hardness and high wear resistance and has higher scratch resistance.

The antifouling coating of the invention is characterized in that a large number of groups such as silica bonds, fluorine-containing groups and the like are connected into the active points of the periodic framework, and various functional groups are orderly arranged in the framework by utilizing the periodic arrangement mode of the framework, so that the free active points are reduced. Meanwhile, the orderly arranged fluorine-containing groups in the fluorosilane can reduce the surface energy of the coating, so that the adsorption of pollutants and the corrosion of chemicals can be reduced, and the coating formed by the coating composition has excellent antifouling property and corrosion resistance.

The antifouling coating of the invention has the advantages that the physical and chemical actions of the active points in the framework, the groups and ions of the coupling agent on the surfaces of the organic and inorganic substrates are realized, the firm combination with the surfaces of the substrates is realized, and the bonding force is higher.

The antifouling coating of the invention is a transparent and wear-resistant antifouling coating. The pencil hardness of the coating can reach 9H, the friction time of 1kg of steel wool is more than 4000 times, the stain is stained for not less than 24 hours, and the color difference delta E of the coating is less than or equal to 1.5. Tolerable stains include, but are not limited to, caustic stains (including but not limited to table vinegar, cola), dye-based stains (including but not limited to dark tea, ink), grease-based stains (including but not limited to animal oils, vegetable oils). The visible light transmittance is more than or equal to 95 percent, and the coating is not damaged and yellow after 1000h of xenon lamp aging acceleration time, and the color difference delta E is less than or equal to 1. The chemical resistance is better than that of C4 grade. After the coating is coated on the surface of the artificial stone, the waterproof performance of the artificial stone is more than or equal to 95 percent. The bonding force cross-hatch method level is better than level 1.

Compared with the artificial stone permeability protective agent, the antifouling coating has better antifouling and antiseptic effects and longer effect duration. Compared with the common protective coating, the coating has good transparency, higher hardness and wear resistance, and can be used on the ground for a long time.

In the antifouling coating of the invention, the PMOS precursor can be self-made or can be a commercial finished product. The structure of the precursor accords with the structure of the PMOS precursor defined by the invention. Based on the structure of the PMOS precursor defined by the invention, under the induction of the structure directing agent, the self-polymerization reaction forms a silica skeleton with periodical arrangement sequence, and the mechanical strength and the stability are superior to those of other silica structures.

In the antifouling coating, the solvent system meets the environmental protection requirement, and the coating is nontoxic and odorless after being completely cured.

According to some embodiments of the invention, the thickness of the anti-fouling coating is 5 μm to 15 μm.

In a fourth aspect, the present invention provides a method for preparing the anti-fouling coating, the method comprising:

and adding a curing agent into the coating composition, uniformly mixing, coating the coating on the surface of a substrate, and drying to obtain the anti-fouling coating.

The invention relates to a technical scheme in a preparation method of an antifouling coating, which at least has the following beneficial effects:

The antifouling coating provided by the invention is easy to construct, has no harsh curing conditions, and is suitable for large-area coating.

According to some embodiments of the invention, the method of preparing the anti-fouling coating may be:

scrubbing the surface of the artificial stone substrate by adopting alcohol and acetone respectively, and then standing for at least half an hour to enable the artificial stone substrate to be sufficiently dried;

After the coupling agent is uniformly mixed with ethanol, uniformly wiping the surface of the base material, and standing for 0.5-1.5 h;

And adding a curing agent into the coating composition, and performing magnetic stirring to fully and uniformly mix, so that subsequent coating preparation operation can be performed. The mass ratio of the coating composition to the curing agent is 6-8:1;

and (3) spraying a transparent wear-resistant antifouling coating on the surface of the substrate, placing after spraying, naturally curing, and then placing in a baking oven at 60-80 ℃ for 6-12 hours to form the transparent wear-resistant antifouling coating.

According to some embodiments of the invention, air spraying is adopted for spraying, and the pressure is 0.2-0.3 MPa.

According to some embodiments of the invention, the spraying distance is 20 mm-30 mm.

According to some embodiments of the invention, the humidity is 40% -60% and the temperature is 15 ℃ -30 ℃.

According to some embodiments of the invention, the coupling agent is at least one of KH550, KH560, a171, a151, and KHA 172.

According to some embodiments of the invention, the curing agent comprises at least one of 3-aminopropyl triethoxysilane and 3-glycidoxypropyl trimethoxysilane.

According to some embodiments of the invention, the curing agent comprises at least one of KH550 and KH 560.

According to some embodiments of the invention, the mass ratio of the curing agent to the coating composition is 1:6-8.

According to some embodiments of the invention, the substrate comprises a cementitious inorganic artificial stone.

In a fifth aspect the invention provides the use of said anti-fouling coating on the surface of a cementitious inorganic artificial stone.

The invention relates to a technical scheme of an antifouling coating applied to the surface of a cement-based inorganic artificial stone, which has at least the following beneficial effects:

The antifouling coating is a transparent and wear-resistant antifouling coating, when the antifouling coating is used on the surface of cement-based inorganic artificial stone, the pencil hardness of the coating can reach 9H, the friction time of 1kg of steel wool is more than 4000 times, the stain is stained for not less than 24h, and the color difference delta E of the coating is less than or equal to 1.5. Tolerable stains include, but are not limited to, caustic stains (including but not limited to table vinegar, cola), dye-based stains (including but not limited to dark tea, ink), grease-based stains (including but not limited to animal oils, vegetable oils). The visible light transmittance is more than or equal to 95 percent, and the coating is not damaged and yellow after 1000h of xenon lamp aging acceleration time, and the color difference delta E is less than or equal to 1. The chemical resistance is better than that of C4 grade. After the coating is coated on the surface of the artificial stone, the waterproof performance of the artificial stone is more than or equal to 95 percent. The bonding force cross-hatch method level is better than level 1.

Drawings

FIG. 1 is an external view of the coating composition prepared in example 1.

Fig. 2 is the results of the abrasion resistance test of the coatings of the examples and comparative examples.

Fig. 3 is the results of the stain resistance test for the coatings of the examples and comparative examples.

Detailed Description

The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.

In some embodiments of the present invention, the present invention provides a coating composition, wherein the raw materials for preparing the coating composition comprise a PMOS precursor, a structure directing agent, a ceramic precursor, an alkoxysilane and a fluorosilane, wherein the functionality of the alkoxysilane is equal to or greater than 2, and the PMOS precursor has a structure as shown in formula (I) or formula (II):

Wherein R ₁ and R ₂ are independently selected from at least one or more of alkane, alkene and amine, and R ₃ is selected from methyl or ethyl.

It will be appreciated that the coating compositions of the present invention, employing PMOS precursors of specific structures, can self-polymerize through the structure directing agent to form a backbone structure having a periodic arrangement. Free active sites remain in the periodic framework, potentially reacting with stains, chemicals. The network skeleton formed by the alkoxy silane with the functionality degree more than or equal to 2 and the ceramic precursor and the free active points are subjected to free radical polymerization reaction, so that inorganic ceramic chemical bonds are inserted into the periodic skeleton formed by the PMOS precursor, the mechanical strength and the stability of the coating structure are enhanced, and the formed coating has the characteristics of high hardness and high wear resistance and has higher scratch resistance.

It can also be appreciated that the coating composition of the present invention reduces free active sites by virtue of the periodic arrangement of the backbone in which a plurality of groups such as siloxane bonds, fluorine-containing groups, etc., are incorporated into the active sites of the periodic backbone. Meanwhile, the orderly arranged fluorine-containing groups in the fluorosilane can reduce the surface energy of the coating, so that the adsorption of pollutants and the corrosion of chemicals can be reduced, and the coating formed by the coating composition has excellent antifouling property and corrosion resistance.

In addition, the active points in the framework of the coating composition of the invention have physical and chemical actions with the groups and ions of the coupling agent on the surfaces of the organic and inorganic substrates, so that the coating composition can be firmly combined with the surfaces of the substrates, and has higher binding force.

It will be appreciated that the coating composition of the present invention, when dried, forms an antifouling coating that is a clear, abrasion resistant antifouling coating. The pencil hardness of the coating can reach 9H, the friction time of 1kg of steel wool is more than 4000 times, the stain is stained for not less than 24 hours, and the color difference delta E of the coating is less than or equal to 1.5. Tolerable stains include, but are not limited to, caustic stains (including but not limited to table vinegar, cola), dye-based stains (including but not limited to dark tea, ink), grease-based stains (including but not limited to animal oils, vegetable oils). The visible light transmittance is more than or equal to 95 percent, and the coating is not damaged and yellow after 1000h of xenon lamp aging acceleration time, and the color difference delta E is less than or equal to 1. The chemical resistance is better than that of C4 grade. After the coating is coated on the surface of the artificial stone, the waterproof performance of the artificial stone is more than or equal to 95 percent. The bonding force cross-hatch method level is better than level 1.

It can be appreciated that the coating composition of the invention, after drying, forms an antifouling coating having better antifouling and preservative effects than the artificial stone permeability protective agent, and the effect duration is longer. Compared with the common protective coating, the coating has good transparency, higher hardness and wear resistance, and can be used on the ground for a long time.

It will be appreciated that the PMOS precursor in the coating composition of the present invention may be either self-made or commercially available. The structure of the precursor accords with the structure of the PMOS precursor defined by the invention. Based on the structure of the PMOS precursor defined by the invention, under the induction of the structure directing agent, the self-polymerization reaction forms a silica skeleton with periodical arrangement sequence, and the mechanical strength and the stability are superior to those of other silica structures.

It will be appreciated that the coating composition of the present invention, the solvent system meets the environmental requirements and the coating is non-toxic and odorless after complete curing.

In some embodiments of the invention, the molecular weight of the PMOS precursor is less than or equal to 10000.

In some embodiments of the present invention, the preparation raw materials include, in parts by weight:

100 parts of PMOS precursor, namely,

0.1 To 0.5 part of structure guiding agent,

50-90 Parts of ceramic precursor,

50-200 Parts of alkoxy silane,

10-20 Parts of fluorosilane.

In some embodiments of the invention, the structure directing agent comprises at least one of a triblock copolymer, cetyltrimethylammonium bromide, cetyltrimethylpyridinium bromide, and alkyltrimethylammonium chloride.

In some embodiments of the invention, the structure directing agent is P123. P123 is a copolymer consisting of three different blocks. It consists of three blocks of polyoxyethylene (EO), polypropylene (PO) and polyethylene (EO), and is therefore also referred to as EO-PO-EO copolymer. The copolymer has two different blocks of hydrophobicity and hydrophilicity, can form microstructures in solution, such as micelle, transparent liquid crystal and the like, is widely applied to the field of material science, and has important application value in the aspects of preparing nano materials, catalysts, drug delivery systems, surface coatings and the like.

In some embodiments of the invention, the ceramic precursor includes at least one of zirconium n-propoxide, ethyl orthosilicate, and butyl n-titanate.

In some embodiments of the present invention, the alkoxysilane includes at least two of methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, 3- [ (2, 3) -glycidoxy ] propylmethyldimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, and dimethyldiethoxysilane.

In some embodiments of the present invention, the fluorosilane comprises at least one of dodecafluoroheptyl propyl trimethoxysilane, perfluorooctyl trimethoxysilane, tridecafluorooctyl triethoxysilane, and heptadecafluorodecyl trimethoxysilane.

In some embodiments of the invention, the preparation raw materials further include, in parts by weight, when the PMOS precursor is 100 parts:

300-500 parts of organic solvent,

10 To 15 parts of catalyst,

30-50 Parts of water.

In some embodiments of the present invention, the organic solvent includes at least one from among methanol, ethanol, n-propanol, and n-butanol.

In some embodiments of the invention, the amount of organic solvent is about 1 to 3 times the total amount of the remaining reagents.

In some embodiments of the invention, the catalyst comprises at least one of an inorganic base, an alkali metal hydroxide, or a metal carboxylate.

In still other embodiments of the present invention, the present invention provides a method of preparing a coating composition comprising the steps of:

Preparing polysiloxane solution by using a structure directing agent, a PMOS precursor, part of organic solvent, a catalyst and water;

Preparing fluorine modified silica sol by utilizing ceramic precursors, alkoxy silane, fluorosilane, partial organic solvent, catalyst and water;

and (3) uniformly mixing the polysiloxane solution and part of the organic solvent, adding fluorine modified silica sol, and refluxing to obtain the coating composition.

It can be appreciated that the preparation method of the coating composition does not need expensive equipment and complex process control, has no harsh reaction conditions, easily available raw materials, low production cost and easy industrial production.

In the preparation method of the coating composition, besides the PMOS precursor, the structure directing agent, the ceramic precursor, the alkoxysilane, the fluorosilane, the organic solvent, the catalyst and the water, other auxiliary agents such as thixotropic agents and wetting agents can be added according to specific requirements, such as specific conditions of construction process and substrate types.

It will be appreciated that one of the functions of the thixotropic agent is to ensure that the coating is able to adapt to different construction processes and to prevent the solid fillers that may be added from settling.

It will also be appreciated that one of the functions of the wetting agent is to ensure good wetting of the substrate with non-uniform surface energy by the coating and rapid leveling.

In some embodiments of the present invention, the thixotropic agent includes a polyurea-type thixotropic agent and a modified polyurea-type thixotropic agent.

In some embodiments of the invention, the wetting agent comprises a silicone-based wetting agent.

In some embodiments of the invention, the polysiloxane solution is prepared by:

a1, uniformly mixing a structure directing agent and part of an organic solvent, uniformly mixing part of a catalyst and water, adding a mixed solution of the catalyst and water into the mixed solution of the structure directing agent and the solvent in a stirring state, adjusting the pH value, and refluxing for 1-1.5 h at 100-120 ℃;

A3, stopping heating, cooling to room temperature under the stirring condition, and performing silica gel column chromatography separation to obtain polysiloxane solution.

In some embodiments of the present invention, the polysiloxane solution may be prepared by:

In some embodiments of the present invention, the mobile phase may be selected from petroleum ether/ethyl acetate system by silica gel column chromatography separation, with a volume ratio of about 50-90:1. The silica gel is 100-200 mesh silica gel.

In some embodiments of the invention, the fluorine modified silica sol is prepared by:

B1, uniformly mixing a ceramic precursor, alkoxy silane and part of organic solvent;

and B3, adding fluorosilane into the mixed solution prepared in the step B2, and continuously refluxing for 1-1.5 h to obtain fluorine modified silica sol.

In some embodiments of the invention, the preparation method of the fluorine modified silica sol can be as follows:

In some embodiments of the present invention, in the preparation method of the coating composition, after uniformly mixing the polysiloxane solution and a part of the organic solvent, adding the fluorine modified silica sol, and refluxing to obtain the coating composition of the present invention, the specific method may be:

In still other embodiments of the present invention, an antifouling coating is provided, resulting from curing the coating composition of the present invention.

It will be appreciated that the anti-fouling coating of the present invention, as it is obtained by curing the coating composition of the present invention, provides at least the full benefit of the coating composition. Specifically:

It will also be appreciated that the antifouling coating of the present invention, the coating employs PMOS precursors of specific structure, which can self-polymerize through the structure directing agent to form a backbone structure with periodic arrangement. Free active sites remain in the periodic framework, potentially reacting with stains, chemicals. The network skeleton formed by the alkoxy silane with the functionality degree more than or equal to 2 and the ceramic precursor and the free active points are subjected to free radical polymerization reaction, so that inorganic ceramic chemical bonds are inserted into the periodic skeleton formed by the PMOS precursor, the mechanical strength and the stability of the coating structure are enhanced, and the formed coating has the characteristics of high hardness and high wear resistance and has higher scratch resistance.

In some embodiments of the invention, the thickness of the anti-fouling coating is 5 μm to 15 μm.

In still other embodiments of the present invention, the present invention provides a method of preparing an anti-fouling coating, comprising:

It can be appreciated that the anti-fouling coating of the present invention is easy to construct, has no severe curing conditions, and is suitable for large-area coating.

In some embodiments of the invention, the method of making the anti-fouling coating may be:

In some embodiments of the invention, the spraying is performed by air, and the pressure is 0.2MPa to 0.3MPa.

In some embodiments of the invention, the spray distance is 20mm to 30mm.

In some embodiments of the invention, the humidity is 40% -60% and the temperature is 15 ℃ -30 ℃.

In some embodiments of the invention, the coupling agent is at least one of KH550, KH560, a171, a151, and KHA 172.

In some embodiments of the invention, the curing agent includes at least one of 3-aminopropyl triethoxysilane and 3-glycidoxypropyl trimethoxysilane.

In some embodiments of the present invention, the curing agent includes at least one of KH550 and KH 560.

In some embodiments of the invention, the mass ratio of the curing agent to the coating composition is 1:6-8.

In some embodiments of the invention, the curing agent is 30 parts to 60 parts by weight when the PMOS precursor is 100 parts by weight.

In some embodiments of the invention, the substrate comprises a cementitious inorganic artificial stone.

In still other embodiments of the present invention, there is provided the use of the anti-fouling coating of the present invention on the surface of a cementitious inorganic artificial stone.

It is understood that the antifouling coating is a transparent and wear-resistant antifouling coating, when the antifouling coating is used on the surface of the cement-based inorganic artificial stone, the pencil hardness of the coating can reach 9H, the friction time of 1kg of steel wool is more than 4000 times, the stain is stained for not less than 24 hours, and the color difference delta E of the coating is less than or equal to 1.5. Tolerable stains include, but are not limited to, caustic stains (including but not limited to table vinegar, cola), dye-based stains (including but not limited to dark tea, ink), grease-based stains (including but not limited to animal oils, vegetable oils). The visible light transmittance is more than or equal to 95 percent, and the coating is not damaged and yellow after 1000h of xenon lamp aging acceleration time, and the color difference delta E is less than or equal to 1. The chemical resistance is better than that of C4 grade. After the coating is coated on the surface of the artificial stone, the waterproof performance of the artificial stone is more than or equal to 95 percent. The bonding force cross-hatch method level is better than level 1.

The technical solution of the present invention will be better understood by combining the following specific embodiments.

Example 1

This example first prepared a coating composition. The specific process is as follows:

preparation of polysiloxane solution in the first step

A1, 20g of ethanol and 0.1g of P123 structure directing agent are uniformly mixed and then introduced into a three-necked flask, and stirring is kept at a rotating speed of about 1750 rpm. After 5g of catalyst (ammonia, CAS number: 7664-41-7) and 15g of deionized water are uniformly mixed, slowly dripping a mixed solution of the catalyst and the deionized water into a three-neck flask under a stirring state, adjusting the pH of the solution to 9 at the dripping speed of about 2.5mL/min, and continuously refluxing for 1.5h at 120 ℃;

A2, the temperature of the solution is reduced to 80 ℃, 30g of ethanol and 27gPMOS precursor (1, 2-bis trimethoxy silicon-based ethane, CAS number: 18406-41-2) are mixed and then added into a three-mouth flask, the dropping speed is about 2.5mL/min, and then the mixture is refluxed for 2 hours at 80 ℃;

A3, stopping heating, keeping magnetic stirring, and performing silica gel column chromatography separation by using (petroleum ether (60-90 ℃) and ethyl acetate=70:1, v/v) as mobile phases after the three-neck flask is air-cooled to room temperature to obtain the polysiloxane solution with the periodic framework structure.

Second step of preparing modified silica sol

B1, uniformly mixing 75g of ethanol, 15g of tetraethoxysilane, 14g of dimethyl diethoxysilane and 24g of methyltrimethoxysilane, putting the mixture into a three-neck flask, magnetically stirring the mixture for 5min, wherein the magnetic stirring speed is about 1750 rpm;

And B2, slowly dripping the mixed solution of the catalyst and the deionized water into the three-neck flask under the stirring state after the catalyst and the deionized water are completely and uniformly stirred, wherein the dripping speed is 2.5mL/min. The pH of the solution was adjusted to 9 and refluxed at 80℃for 1h;

B3, then, dropwise adding 5g of tridecafluorooctyl triethoxysilane into the three-necked flask, wherein the dropwise adding speed is 3mL/s, and keeping the temperature for continuous reflux for 2h. Obtaining fluorine modified silica sol.

Third step, preparing transparent wear-resistant antifouling paint

C1, uniformly mixing 20g of ethanol and polysiloxane solution, and placing the mixture into a three-neck flask, and keeping magnetic stirring for 5min. The magnetic stirring speed is 1750rpm;

c2, then, the fluorine modified silica sol was added dropwise to the three-necked flask at a dropping rate of 3mL/s. And refluxed at 80 ℃ for 1.5h;

And C3, finally, filtering the prepared solution through a 200-mesh copper mesh to obtain the transparent wear-resistant antifouling paint. As shown in fig. 1, it can be seen that the antifouling paint according to the embodiment of the present invention is clear and transparent in appearance.

Then, an antifouling coating is prepared on the surface of the cement-based inorganic artificial stone. The specific process is as follows:

D1, scrubbing the surface of the artificial stone substrate by adopting alcohol and acetone respectively, and standing for half an hour to fully dry the artificial stone substrate;

d2, uniformly mixing KH550 and alcohol (1:1 volume ratio), uniformly wiping the surface of the artificial stone substrate, and standing for 1h;

d3, adding 7g of 3-aminopropyl triethoxysilane into 49g of the prepared transparent wear-resistant antifouling paint, magnetically stirring for 5min, and fully and uniformly mixing, so that subsequent coating preparation operation can be performed;

And D4, spraying transparent wear-resistant antifouling paint on the surface of the artificial stone, wherein the spraying is performed by air, the pressure is 0.25MPa, and the spraying distance is about 25 mm. The humidity is about 50%. The temperature is about 20 ℃. And (3) after the spraying is finished, placing for 30min, naturally curing, and then placing into an oven at 80 ℃ to bake for 12h to obtain the transparent wear-resistant antifouling coating.

Example 2

preparation of polysiloxane solution in the first step

A1, 20g of ethanol and 0.1g of P123 structure directing agent are uniformly mixed and then introduced into a three-necked flask, and stirring is kept at a rotating speed of about 1750 rpm. Uniformly mixing 5g of catalyst (ammonia, CAS number: 7664-41-7) and 15g of deionized water, slowly dripping a mixed solution of the catalyst and the deionized water into a three-neck flask under a stirring state, adjusting the pH of the solution to 9-10 at the dripping speed of about 2-3mL/min, and continuously refluxing at 120 ℃ for 1h;

a2, the temperature of the solution is reduced to 60 ℃, 8g of ethanol and 30gPMOS precursor (1, 1-bis (trimethoxysilylmethyl) ethylene with CAS number of 143727-20-2) are mixed and then added into a three-mouth flask, the dropping speed is about 2-3mL/min, and then the mixture is refluxed for 3 hours;

A3, stopping heating, keeping magnetic stirring, removing the prepared solution after the three-neck flask is air-cooled to room temperature, and performing silica gel column chromatography separation by using (petroleum ether (60-90 ℃) and ethyl acetate=70:1, v/v) as mobile phases to obtain the polysiloxane solution with the periodic framework structure.

Second step of preparing modified silica sol

B1, uniformly mixing 20g of ethanol, 20g of tetraethoxysilane, 14g of dimethyl diethoxysilane, 18g of phenyl trimethoxysilane and 14g of methyl trimethoxysilane, putting into a three-neck flask, magnetically stirring for 5min, wherein the magnetic stirring speed is about 1750 rpm;

and B2, slowly dripping the mixed solution of the catalyst and the deionized water into the three-neck flask under the stirring state after the catalyst and the deionized water are completely and uniformly stirred, wherein the dripping speed is 2.5mL/min. The solution pH was adjusted to 9 and refluxed at 60 ℃ for 1.5h;

b3. Then, 6g of dodecafluoroheptyl propyl trimethoxysilane was added dropwise to the three-necked flask at a dropping rate of 3mL/s. The temperature was maintained for a further 2h under reflux. Obtaining fluorine modified silica sol.

Third step, preparing transparent wear-resistant antifouling paint

C1, uniformly mixing 20g of ethanol and polysiloxane solution, and placing the mixture into a three-neck flask, and keeping magnetic stirring for 5min. The magnetic stirring speed is about 1750 rpm;

C2, then, the fluorine modified silica sol was added dropwise to the three-necked flask at a dropping rate of about 3 mL/s. And refluxed at 60 ℃ for 1.5 hours;

And C3, finally, filtering the prepared solution through a 200-mesh copper mesh to obtain the transparent wear-resistant antifouling paint.

d2, uniformly mixing KH550 and alcohol (1:1), uniformly wiping the surface of the artificial stone substrate, and standing for 1h;

Comparative example 1

The main difference between this comparative example and example 1 is that no poly PMOS precursor solution was added.

The preparation process comprises the following steps:

(1) Mixing 60g of ethanol, 15g of tetraethoxysilane, 14g of dimethyl diethoxysilane and 24g of methyltrimethoxysilane uniformly, putting into a three-neck flask, and magnetically stirring for 5min at 1750rpm;

(2) After completely stirring uniformly, a mixed solution of 5g of catalyst (ammonia, CAS number: 7664-41-7) and 15g of deionized water was slowly dropped into the three-necked flask under stirring at an acceleration of 2.5mL/min. The pH of the solution was adjusted to 9 and refluxed at 80℃for 1h;

(3) Then 5g of tridecafluorooctyltriethoxysilane was added dropwise to the three-necked flask at a rate of 2-4mL/s. The temperature was maintained for a further 2h under reflux. Obtaining fluorine modified silica sol;

(4) Finally, filtering the prepared solution through a 200-mesh copper mesh to obtain a transparent wear-resistant antifouling paint;

(5) Scrubbing the surface of the artificial stone substrate by adopting alcohol and acetone respectively, and standing for half an hour to fully dry the artificial stone substrate;

(6) Uniformly mixing KH550 and alcohol (1:1), uniformly wiping the surface of the artificial stone substrate, and standing for 1h;

(7) And adding 7g of 3-aminopropyl triethoxysilane into 49g of the prepared transparent wear-resistant antifouling paint, magnetically stirring for 5min, and fully and uniformly mixing to obtain the paint composition.

and spraying a transparent wear-resistant antifouling paint on the surface of the artificial stone, wherein the spraying is performed by air, the pressure is 0.25MPa, and the spraying distance is about 25 mm. The humidity is about 50%. The temperature is about 20 ℃. And (3) after the spraying is finished, standing for 30min, naturally curing, and then putting into an oven at 80 ℃ to bake for 12h to obtain the coating.

Comparative example 2

The main difference between this comparative example and example 2 is that the silica sol was not modified with fluorine.

The preparation process comprises the following steps:

(1) 60g of ethanol and 0.1g of P123 structure directing agent were uniformly mixed and introduced into a three-necked flask, and stirring was maintained.

The rotation speed is about 1750 rpm;

(2) After 5g of catalyst (ammonia, CAS number 7664-41-7) and 15g of deionized water were mixed uniformly. Slowly dripping the mixed solution of the catalyst and the deionized water into the three-neck flask under the stirring state, wherein the dripping speed is 2.5mL/min. Adjusting the pH of the solution to 9, and continuously refluxing at 120 ℃ for 1h;

(3) The temperature of the solution was reduced to 60℃and 6g of ethanol, 34gPMOS of the precursor (bis (3-trimethoxysilylpropyl), CAS number 82985-35-1) were mixed and added to the three-necked flask. The dropping speed was about 2.5 mL/min.

Then refluxing for 3 hours;

(4) Then stopping heating, keeping magnetic stirring, removing the prepared solution after the three-neck flask is air-cooled to room temperature, and performing silica gel column chromatography separation by using (petroleum ether (60-90 ℃) ethyl acetate=70:1, v/v) as a mobile phase to obtain a polysiloxane solution with a periodic framework structure;

(5) Finally, filtering the prepared solution through a 200-mesh copper mesh to obtain a transparent wear-resistant antifouling paint;

(6) Scrubbing the surface of the artificial stone substrate by adopting alcohol and acetone respectively, and standing for half an hour to fully dry the artificial stone substrate;

(7) KH550 and alcohol (1:1) were uniformly mixed, and then the mixture was uniformly wiped over the surface of the artificial stone substrate, followed by standing for 1 hour.

(8) And adding 7g of 3-aminopropyl triethoxysilane into 49g of the prepared transparent wear-resistant antifouling paint, magnetically stirring for 5min, and fully and uniformly mixing to obtain the paint composition.

And spraying a transparent wear-resistant antifouling paint on the surface of the artificial stone, wherein the spraying is performed by air, the pressure is about 0.25MPa, and the spraying distance is about 25 mm. The humidity is about 50%. The temperature was all at 20 ℃. And (3) after the spraying is finished and the coating is placed for 30min for natural curing, placing the coating into an oven at 80 ℃ for baking for 12h, and obtaining the transparent wear-resistant antifouling coating.

Comparative example 3

A coating composition was prepared first in this comparative example. The specific process is as follows:

preparation of polysiloxane solution in the first step

A1, 20g of ethanol and 58gPMOS of precursor (N- [ vinyl-bis (3-trimethoxysilylpropylamino) silane group ] -3-trimethoxysilylpropane-1-amine, CAS number: 112667-69-3) are uniformly mixed and then introduced into a three-neck flask, and stirring is kept at a rotating speed of about 1750 rpm. After 5g of catalyst (ammonia, CAS number: 7664-41-7) and 15g of deionized water are uniformly mixed, slowly dripping a mixed solution of the catalyst and the deionized water into a three-neck flask under a stirring state, adjusting the pH of the solution to 11 at the dripping speed of about 2.5mL/min, and continuously refluxing for 1.5h at 80 ℃;

a2, mixing 6g of ethanol and 0.1g of P123 structure directing agent, adding into a three-neck flask, dropping the mixture at the speed of about 6mL/min, and then cooling to 40 ℃ for reflux for 4h;

A3, stopping heating, keeping magnetic stirring, removing the prepared solution after the three-neck flask is air-cooled to room temperature, and performing silica gel column chromatography separation by using (petroleum ether (60-90 ℃) and ethyl acetate=70:1, v/v) as a mobile phase to obtain the polysiloxane solution with the periodic framework structure.

Second step of preparing modified silica sol

B1, uniformly mixing 20g of ethanol, 15g of tetraethoxysilane, 14g of dimethyl diethoxysilane and 24g of methyltrimethoxysilane, putting into a three-neck flask, magnetically stirring for 5min, wherein the magnetic stirring speed is about 1250 rpm;

and B2, slowly dripping the mixed solution of the catalyst and the deionized water into the three-neck flask under the stirring state after the catalyst and the deionized water are completely and uniformly stirred, wherein the dripping speed is 6mL/min. The solution pH was adjusted to 9 and refluxed at 40 ℃ for 3h.

B3. Then, 5g of tridecafluorooctyltriethoxysilane was added dropwise to the three-necked flask at a dropping rate of 3mL/s. The temperature was maintained at reflux for 1h. Obtaining fluorine modified silica sol.

Third step, preparing transparent wear-resistant antifouling paint

C1, uniformly mixing 20g of ethanol and fluorine modified silica sol, and placing the mixture into a three-neck flask, and keeping magnetic stirring for 5min. The magnetic stirring speed is 1750rpm;

C2 subsequently, the polysiloxane solution was added dropwise to the three-necked flask at a dropping rate of 3mL/s. And refluxed at 100 ℃ for 0.5h;

And D1, scrubbing the surface of the artificial stone substrate by adopting alcohol and acetone respectively, and standing for half an hour to enable the artificial stone substrate to be sufficiently dried.

And D2, uniformly mixing KH550 and alcohol (1:1), uniformly wiping the surface of the artificial stone substrate, and standing for 1h.

And D3, adding 7g of 3-aminopropyl triethoxysilane into 49g of the prepared transparent wear-resistant antifouling paint, magnetically stirring for 5min, and fully and uniformly mixing, so that the subsequent coating preparation operation can be performed.

And D4, spraying transparent wear-resistant antifouling paint on the surface of the artificial stone, wherein the spraying is performed by air, the pressure is 0.25MPa, and the spraying distance is about 25 mm. The humidity was 50%. The temperature was 20 ℃. And (3) after the spraying is finished, placing for 30min, naturally curing, and then placing into an oven at 80 ℃ to bake for 12h to obtain the transparent wear-resistant antifouling coating.

Test case

The coatings prepared in examples and comparative examples were tested for pencil hardness, adhesion, abrasion resistance, stain resistance, chemical resistance, water resistance, weather resistance and transmittance. Wherein:

the pencil hardness test is based on the standard GB/T6739-2006 "paint film hardness is measured by the method of colored paint and varnish pencil".

The adhesion test is based on the standard GB/T9286-2021 cross-cut test of paint films of color paints and varnishes.

The abrasion resistance test is based on the standard of GB/T22374-2018 "floor decorating material", and the abrasion resistance test method adopts 0000# steel wool to carry out reciprocating friction on the surface of the coating under the load of 1Kg, the friction frequency is 1Hz, and the friction length is about 50mm. The number of rubs was 4000 times and the appearance of the coating after abrasion was observed.

The standard of the stain resistance test is JC/T908-2013 stain resistance test part of artificial stone, and a color difference meter measures the color difference between a polluted place and an uncontaminated place as a test result.

The standard for testing the chemical resistance is GBT35157-2017 resin type synthetic stone slab.

The standard of the waterproof performance test basis is JC/T973-2005 annex A of industry Standard of Natural Stone protectant for architectural decoration.

The weather resistance test is based on the standard GB/T1865-2009 (Manual weathering of paints and varnishes and exposure of artificial radiation to filtered xenon arc radiation).

The standard of the transmittance test basis is the visible light wave band in GB 5433-2008 "daily glass transmittance determination method".

The test results are shown in Table 1.

TABLE 1 coating Performance test results

Test item	Example 1	Example 2	Comparative example 1	Comparative example 2	Comparative example 3
						Hardness of pencil	9H	9H	5H	4H	6H
Adhesion force	Level 0	Level 0	Is better than grade 1	Is better than grade 1	Is better than grade 1
						Wear resistance	Is not thoroughly ground	Is not thoroughly ground	Exposing the substrate	Exposing the substrate	Exposing the substrate
Stain resistance	ΔE≤1.5	ΔE≤1.5	ΔE≤4	ΔE≤7	ΔE≤6
						Chemical resistance	Is better than C4	Is better than C4	Is better than C2	Is better than C3	Is better than C2
Waterproof property	≥95%	≥95%	≥80%	≥90%	≥85%
						Weather resistance	ΔE≤1	ΔE≤1	ΔE≤3	ΔE≤3	ΔE≤3
Transmittance of light	95%	95%	95%	95%	95%
						Film thickness	8.5μm	7.9μm	11.2μm	9.2μm	8.4μm

As can be seen from the test results of Table 1, the coating composition of the present invention, after drying, forms an antifouling coating that is transparent and abrasion resistant.

The pencil hardness of the coating can reach 9H.

The friction times of 1kg steel wool are more than 4000. The results of the abrasion resistance test of the coatings of the examples and comparative examples are shown in fig. 2.

The stain is stained for not less than 24 hours. The results of the stain resistance test of the coatings of the examples and comparative examples are shown in fig. 3.

The color difference delta E of the coating is less than or equal to 1.5.

Tolerable stains include, but are not limited to, caustic stains (including but not limited to table vinegar, cola), dye-based stains (including but not limited to dark tea, ink), grease-based stains (including but not limited to animal oils, vegetable oils).

The visible light transmittance is more than or equal to 95 percent.

After 1000h of xenon lamp aging acceleration time, the coating is not damaged and yellow, and the color difference delta E is less than or equal to 1.

The chemical resistance is better than that of C4 grade.

After the coating is coated on the surface of the artificial stone, the waterproof performance of the artificial stone is more than or equal to 95 percent.

The bonding force cross-hatch method can reach 0 level.

In comparative example 3, the addition sequence, the addition speed, the proportion and the like of the raw materials are different, so that the PMOS precursor is not crosslinked or is not crosslinked completely to form a three-dimensional network framework structure in the preparation process, the hardness of the coating is reduced, and meanwhile, the free active points in the structure are more, so that the performances such as chemical resistance and weather resistance are reduced. Reactive sites that are not fully crosslinked also compete for the fluorine modified solution, which in turn results in a reduced content of active species in the coating. More other substances or active substances, and thus the coating properties are reduced. Meanwhile, if the active substances remained in the polysiloxane solution are more and compete for active groups added into the fluorine modified solution, so that the components of the active substances in the whole coating are less, and other low-performance substances are increased, so that the coating performance is reduced.

The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.

Claims

1. The coating composition is characterized in that the preparation raw materials comprise a PMOS precursor, a structure guiding agent, a ceramic precursor, alkoxysilane and fluorosilane, wherein the functionality of the alkoxysilane is more than or equal to 2, and the PMOS precursor has a structure shown as a formula (I) or a formula (II):

Wherein, R ₁ and R ₂ are independently selected from at least one of alkane, alkene and amine, and R ₃ is selected from methyl or ethyl;

the coating composition is prepared by the following method:

preparing polysiloxane solution by using the structure directing agent, the PMOS precursor, the organic solvent, the catalyst and water;

preparing fluorine modified silica sol by using the ceramic precursor, alkoxy silane, fluorosilane, an organic solvent, a catalyst and water;

uniformly mixing the polysiloxane solution and an organic solvent, adding the fluorine modified silica sol, and refluxing to obtain the coating composition;

the preparation method of the polysiloxane solution comprises the following steps:

A1, uniformly mixing the structure directing agent and an organic solvent, uniformly mixing a catalyst and water, adding a mixed solution of the catalyst and water into the mixed solution of the structure directing agent and the solvent in a stirring state, adjusting the pH value, and refluxing for 1-1.5 h at 100-120 ℃;

A2, cooling the solution prepared in the step A1 to 60-80 ℃, mixing an organic solvent and the PMOS precursor, adding the mixture into the cooled solution prepared in the step A1, and refluxing for 2-3 hours;

A3, stopping heating, cooling to room temperature under the stirring condition, and performing silica gel column chromatography separation to obtain the polysiloxane solution;

the structure directing agent comprises at least one of triblock copolymer, cetyltrimethylammonium bromide, cetyltrimethyl pyridinium bromide and alkyltrimethylammonium chloride;

The ceramic precursor comprises at least one of zirconium n-propoxide, ethyl orthosilicate and butyl n-titanate.

2. The coating composition of claim 1, wherein the preparation raw materials comprise, in parts by weight:

100 parts of PMOS precursor, namely,

0.1 To 0.5 part of structure guiding agent,

50-90 Parts of ceramic precursor,

50-200 Parts of alkoxy silane,

10-20 Parts of fluorosilane.

3. The coating composition of claim 1, wherein the alkoxysilane comprises at least two of methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, 3- [ (2, 3) -glycidoxy ] propylmethyldimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, and dimethyldiethoxysilane.

4. The coating composition of claim 1, wherein the fluorosilane comprises at least one of dodecafluoroheptyl propyl trimethoxysilane, perfluorooctyl trimethoxysilane, tridecafluorooctyl triethoxysilane, and heptadecafluorodecyl trimethoxysilane.

5. The coating composition according to any one of claims 1 to 4, wherein the preparation raw materials further comprise, in parts by weight, when the PMOS precursor is 100 parts:

300-500 parts of organic solvent,

10 To 15 parts of catalyst,

30-50 Parts of water.

6. The coating composition of claim 5, wherein the organic solvent comprises at least one from the group consisting of methanol, ethanol, n-propanol, and n-butanol.

7. The coating composition of claim 5, wherein the catalyst comprises at least one of an inorganic base, an alkali metal hydroxide, or a metal carboxylate.

8. The coating composition of claim 1, wherein the fluorine modified silica sol is prepared by a process comprising:

B1, uniformly mixing the ceramic precursor, the alkoxy silane and the organic solvent;

B2, uniformly mixing the catalyst and water, adding the mixed solution of the catalyst and the water into the mixed solution prepared in the step B1 under the stirring state, adjusting the pH value, and refluxing for 1-1.5 h at 60-80 ℃;

9. An antifouling coating layer, characterized in that it is obtained by curing the coating composition according to any one of claims 1 to 8.

10. Use of an anti-fouling coating according to claim 9 on the surface of a cement-based inorganic artificial stone.