CN114058223B - Durable antibacterial antiviral super-amphiphobic coating and preparation method thereof - Google Patents
Durable antibacterial antiviral super-amphiphobic coating and preparation method thereof Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a durable antibacterial antiviral super-amphiphobic coating and a preparation method thereof, wherein the coating comprises a primer coated on the surface of a substrate and a finish paint attached to the primer, the raw materials of the primer comprise fluorine-containing resin, acrylic resin, inorganic filler, solvent A1 and an auxiliary agent, and the raw materials of the finish paint comprise super-hydrophobic super-oleophobic modified nano-silica, nano-silver and solvent A2. The coating has simple preparation process, simultaneously has the functions of hydrophobicity, oleophobicity, antibiosis and antivirus, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a durable antibacterial antiviral super-amphiphobic coating and a preparation method thereof.
Background
In recent years, the new coronavirus wraps the world, so that the global public health safety is destroyed unprecedentedly, and people have unprecedentedly strong consciousness on prevention and control of the virus. Under the large background, public health and safety are more and more emphasized by people, and bacteria serving as one of old organisms are easy to breed and propagate on the surfaces of objects, so that the life and health of human beings are seriously threatened. Accordingly, surface materials that are effective in inhibiting bacterial growth, effective in killing bacteria, and effective in combating viruses are also attracting increasing attention.
The durable antibacterial antiviral super-amphiphobic coating is an important application material, has unique super-hydrophobic, super-oleophobic and self-cleaning functions of the super-amphiphobic coating, and enables bacteria to have less breeding environment on the surface of the material to play a role in inhibiting bacteria; the surface of the durable antibacterial antiviral super-amphiphobic coating contains superfine nano-silver, and the Ag can be slowly released + And the thiol-group-containing antibacterial agent can be diffused to a mycoderm, can strongly combine the thiol group of zymoprotein to inactivate enzyme, and has stronger bactericidal action; ultrafine nanometer in durable antibacterial/antiviral super-amphiphobic coatingSilver has strong adsorption and fixation effects on viruses, and can prevent the viruses from entering host cells, so that the viruses lose survival conditions and die. In addition, the nano silver can be combined with nucleic acid of the virus, so that the DNA or RNA structure of the virus is changed and inactivated. The surface of the durable antibacterial and antiviral super-amphiphobic coating material has excellent antibacterial, bactericidal and antiviral properties, so that long-term antibacterial and antiviral effects are realized.
However, the coating in the prior art is difficult to have the super-hydrophobic and super-oleophobic functions at the same time, and the bonding strength between the hydrophobic and oleophobic material and the coating is poor, so that the coating fails.
Disclosure of Invention
In view of the above, the invention provides a durable antibacterial antiviral super-amphiphobic coating, which is simple in preparation process and has hydrophobic, oleophobic, antibacterial and antiviral functions.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the durable antibacterial antiviral super-amphiphobic coating comprises a primer coated on the surface of a substrate and a finish paint attached to the primer, wherein the primer raw material comprises fluorine-containing resin, acrylic resin, inorganic filler, a solvent A1 and an auxiliary agent, and the finish paint raw material comprises super-hydrophobic and super-oleophobic modified nano silicon dioxide, nano silver and a solvent A2.
Preferably, the primer raw material comprises 20-30% of fluorine-containing resin, 10-15% of acrylic resin, 12-20% of inorganic filler, 20-30% of solvent and the balance of auxiliary agent by weight percentage.
Preferably, the inorganic filler comprises 10 to 15 percent of 10 to 50 μm inorganic filler B1 and 2 to 5 percent of 80 to 110 μm inorganic filler B2 in percentage by weight. More preferably, the inorganic filler B1 and the inorganic filler B2 are both barium sulfate powder. It is to be understood that the inorganic filler B1 and the inorganic filler B2 may be the same substance or different substances.
Preferably, the solvent A1 is at least one of volatile organic solvents such as ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, and ethanol.
Preferably, the auxiliary agent is at least 3 of defoaming agent, cosolvent, dispersant and diluent; suitable auxiliaries serve to strengthen the bond between the resin and the inorganic particles in the primer, and the bond between the primer and the topcoat.
Preferably, the finishing paint raw materials comprise 5-10% of nano silicon dioxide, 80-90% of absolute ethyl alcohol and the balance of nano silver according to weight ratio; the particle size of the nano silicon dioxide is 10-1000 nm, the particle size of the nano silver is 20-100 nm, and the wider size distribution of the silicon dioxide particles is beneficial to the dispersion of the superfine nano silver in the silicon dioxide particles, so that the nano silver is better embedded into the coating when the nano silver is solidified into a film.
Preferably, the preparation process of the super-hydrophobic and super-oleophobic modified nano-silica comprises the following steps: sequentially adding an alcohol solvent, a basic catalyst and silicate ester into a reactor according to the mass ratio of 30-50, namely, 0.1-2.0; adding fluorine-containing organic matter with the mass ratio of 0.1-1.0 into a reactor, and continuously reacting for 8 hours at the temperature of 50-70 ℃ to obtain super-hydrophobic and super-oleophobic SiO 2 A nanoparticle;
the alkaline catalyst is ammonia water;
the alcohol solvent is one or more of ethanol, methanol and isopropanol, and preferably ethanol is adopted;
the silicate is one or two of tetrabutyl orthosilicate and tetraethyl orthosilicate;
the fluorine-containing organic matter comprises one or more of perfluorodecyl triethoxysilane, perfluorooctyl triethoxysilane, perfluorodecyl trimethoxysilane and perfluorooctyl trimethoxysilane.
Preferably, the fluorine-containing resin is a fluorine-carbon resin.
The invention also provides a method for preparing the durable antibacterial antiviral super-amphiphobic coating, which comprises the following steps: uniformly mixing and dispersing the primer raw materials, spraying the mixture on the surface of a substrate, and drying the surface of a primer coating after 5-30 min; and (3) uniformly mixing and dispersing the finishing paint raw materials, spraying the finishing paint raw materials on the primer, and curing at room temperature.
The invention has the beneficial effects that:
1) The modified nano-silica particles in the finish paint have the super-hydrophobic and super-oleophobic functions simultaneously, and the modified nano-silica particles in the finish paint and the primer have enough bonding strength by matching with an organic system formed by fluorocarbon resin and acrylic resin, so that the failure of the coating caused by the falling-off of the modified nano-silica particles is effectively avoided;
2) The inorganic filler in the primer at least comprises two different particle sizes, so that the requirement of the conventional filler can be met, the micro-nano structure roughness of the surface of the primer is effectively improved, and the embedding strength of the modified nano silicon dioxide and the nano silver in the finish paint is improved;
3) The size range of the modified nano silicon dioxide particles is far wider than that of the nano silver particles, so that the nano silver can be well dispersed and fixed in the finish paint, the slow release effect of the nano silver is improved, and the antibacterial and antiviral validity periods are effectively improved;
4) The water static contact angle of the durable antibacterial/antiviral super-amphiphobic coating prepared by the invention can reach 160 degrees, and the water rolling angle is less than 2 degrees; the static contact angle of the pump oil can reach 155 degrees, and the rolling angle of the pump oil is 5 degrees; the ultraviolet aging test of the coating is circulated for 1000 hours, and the antibacterial/antiviral super-amphiphobic performance is not changed; the antibacterial rate of the coating on escherichia coli reaches 99.95%, and the antibacterial rate on golden glucose spheres reaches 99.97%;
5) The preparation process is simple and the effective period is long.
Drawings
FIG. 1 is a schematic structural diagram of a durable antibacterial antiviral super-amphiphobic coating prepared by the invention
Detailed Description
In order to better understand the present invention, the following embodiments are further illustrated, but the present invention is not limited to the following embodiments.
Example 1
Mixing 20% of fluorine-carbon resin, 10% of acrylic resin, 10% of 10-50 μm of barium sulfate powder, 5% of 80-110 μm of barium sulfate powder, 25% of butyl acetate, 5% of cosolvent, 15% of diluent, 5% of dispersing agent and 5% of defoaming agent according to weight percentage, and dispersing for 30min at the room temperature at 800r/min to obtain the primer for later use. In this example, the cosolvent is n-butanol, the diluent is propylene glycol methyl ether acetate, the dispersant is BYK161, and the defoamer is an organosilicon defoaming polymer.
Mixing 5% of super-amphiphobic modified nano silicon dioxide particles, 90% of absolute ethyl alcohol and 5% of superfine nano silver powder, and dispersing at room temperature for 30min at 1500r/min to obtain finish paint for later use. The preparation process of the super-amphiphobic modified nano silica particles can be referred to as ZL201810777178.5, and is not described herein again.
And uniformly spraying the primer on the glass substrate by using an air spray gun, spraying the finish paint on the primer after 5min, and standing at room temperature for 48h to obtain the durable antibacterial/antiviral super-amphiphobic coating.
Example 2
Mixing 25% of fluorine-carbon resin, 12.5% of acrylic resin, 12.5% of barium sulfate powder accounting for 10-50 μm, 4% of 80-110 μm of barium sulfate powder, 25% of ethyl acetate, 5% of cosolvent, 7.5% of diluent, 6% of dispersing agent and 2.5% of defoaming agent according to weight percentage, and dispersing at room temperature for 30min at 800r/min to obtain the primer for later use.
7.5 percent of super-amphiphobic modified nano silicon dioxide particles (also in the embodiment 1), 85 percent of absolute ethyl alcohol and 7.5 percent of superfine nano silver powder are mixed and dispersed for 30min at the room temperature at 1500r/min to obtain finish paint for later use.
And uniformly spraying the primer on the glass substrate by using an air spray gun, spraying the finish paint on the primer after 5min, and standing at room temperature for 48h to obtain the durable antibacterial/antiviral super-amphiphobic coating.
Example 3
Mixing 30% of fluorine-carbon resin, 10% of acrylic resin, 15% of barium sulfate powder accounting for 10-50 mu m, 5% of 80-110 mu m of barium sulfate powder, 30% of propylene glycol methyl ether acetate, 2.5% of cosolvent, 2.5% of diluent, 2.5% of dispersing agent and 2.5% of defoaming agent according to weight percentage, and dispersing for 30min at the room temperature of 800r/min to obtain a primer for later use;
mixing 10% of super-amphiphobic modified nano silicon dioxide particles (in the same time, the embodiment 1), 85% of absolute ethyl alcohol and 5% of superfine nano silver powder, and dispersing at the room temperature of 1500r/min for 30min to obtain finish paint for later use.
And uniformly spraying the primer on the glass substrate by using an air spray gun, spraying the finish paint on the primer after 5min, and standing at room temperature for 48h to obtain the durable antibacterial/antiviral super-amphiphobic coating.
Comparative example 1
According to weight percentage, 20 percent of fluorine-silicon resin, 30 percent of acrylic resin, 10 percent to 50 mu m of barium sulfate powder, 5 percent of 80 to 110 mu m of barium sulfate powder, 30 percent of propylene glycol methyl ether acetate, 5 percent of cosolvent, 2.5 percent of dispersant and 2.5 percent of defoamer are mixed, and are dispersed for 30min at the room temperature of 800r/min to obtain the primer for standby.
Mixing 10% of super-amphiphobic modified nano silicon dioxide particles (in the same time, the embodiment 1), 80% of absolute ethyl alcohol and 10% of superfine nano silver powder, and dispersing at the room temperature of 1500r/min for 30min to obtain finish paint for later use.
And uniformly spraying the primer on the glass substrate by using an air spray gun, spraying the finish paint on the primer after 5min, and standing at room temperature for 48h to obtain the durable antibacterial/antiviral super-amphiphobic coating.
Comparative example 2
Mixing 40% of acrylic resin, 15% of 10-50 μm barium sulfate powder, 5% of 80-110 μm barium sulfate powder, 25% of propylene glycol methyl ether acetate, 5% of cosolvent, 7.5% of dispersant and 2.5% of defoamer according to weight percentage, and dispersing at the room temperature for 30min at 800r/min to obtain the primer for later use.
5 percent of super-amphiphobic modified nano silicon dioxide particles, 90 percent of absolute ethyl alcohol and 5 percent of superfine nano silver powder are mixed and dispersed for 30min at room temperature at 1500r/min to obtain finish paint for later use.
And uniformly spraying the primer on the glass substrate by using an air spray gun, spraying the finish paint on the primer after 5min, and standing at room temperature for 48h to obtain the durable antibacterial/antiviral super-amphiphobic coating.
Comparative example 3
According to weight percentage, 30 percent of fluorine-carbon resin, 10 percent of acrylic resin, 20 percent of 10-50 mu m barium sulfate powder, 25 percent of propylene glycol methyl ether acetate, 5 percent of cosolvent, 7.5 percent of dispersant and 2.5 percent of defoamer are mixed, and are dispersed for 30min at the room temperature at 800r/min to obtain the primer for standby.
Mixing 2.5% of super-amphiphobic modified nano silicon dioxide particles, 90% of absolute ethyl alcohol and 7.5% of superfine nano silver powder, and dispersing at room temperature for 30min at 1500r/min to obtain finish paint for later use.
And uniformly spraying the primer on the glass substrate by using an air spray gun, spraying the finish paint on the primer after 5min, and standing at room temperature for 48h to obtain the durable antibacterial/antiviral super-amphiphobic coating.
Comparative example 4
According to weight percentage, 30 percent of fluorine-carbon resin, 10 percent of acrylic resin, 15 percent of 10-50 mu m barium sulfate powder, 5 percent of 80-110 mu m barium sulfate powder, 10 percent of butyl acetate, 15 percent of propylene glycol monomethyl ether acetate, 5 percent of cosolvent, 7.5 percent of dispersant and 2.5 percent of defoamer are mixed, and are dispersed for 30min at the room temperature of 800r/min to obtain the primer for standby.
Mixing 10% of super-amphiphobic modified nano silicon dioxide particles (the particle size is 10-100 nm), 85% of absolute ethyl alcohol and 5% of superfine nano silver powder, and dispersing at room temperature at 1500r/min for 30min to obtain finish paint for later use.
And uniformly spraying the primer on the glass substrate by using an air spray gun, spraying the finish paint on the primer after 5min, and standing at room temperature for 48h to obtain the durable antibacterial/antiviral super-amphiphobic coating.
Comparative example 5
The super-hydrophobic coating of a certain brand of the most advanced U.S. is purchased, and the coating is soft and has excellent super-hydrophobic performance.
Comparative example 6
Certain brands of antimicrobial coatings are commercially available, which have excellent antimicrobial properties.
Comparing the super-hydrophobic performance, the super-oleophobic performance, the durability and the antibacterial performance of all coating samples, and obtaining results shown in table 1, wherein the aging experimental method is carried out according to the cycle A regulation in GB/T1865-2009 color paint and varnish artificial climate aging and artificial radiation exposure; the antibacterial detection method refers to GB/T21866-2008 'antibacterial property determination method and antibacterial effect of antibacterial coating (paint film)'.
TABLE 1
As can be seen from table 1, the coating obtained according to the weight ratio and the preparation scheme of the present invention has excellent super-hydrophobic, super-oleophobic, antibacterial property and durability characteristics.
After an aging test, the hydrophobic, oleophobic and antibacterial properties of the coatings of the comparative examples 1, 2 and 3 are deteriorated, which shows that the nano particles in the finish paint fall off to a certain degree, and proves that the bonding strength of the finish paint material and the primer is poor; the coatings of comparative examples 1 and 2 show skinning, indicating that the organic system in the primer has poor weatherability and has not achieved the basic properties of the coating.
Comparing example 3 with comparative example 4, it is found that when the nano-silica in the super-amphiphobic coating is close to the nano-silver particles, the antibacterial performance is obviously reduced after a period of time, and the size of the nano-silica has a significant influence on the antibacterial durability of the nano-silver.
Comparing example 1 with comparative example 5, it is found that comparative example 5 has only hydrophobic property, the antibacterial effect of the coating on escherichia coli and staphylococcus aureus is general, and the hydrophobic property and the antibacterial property of the coating are obviously reduced after the 1000-hour aging test. The main reason is that the comparative example 5 only has hydrophobic property, and can not repel organic substances such as oil stains in nature, so that bacteria can breed on the surface of the coating, the single super-hydrophobic property is poor in ultraviolet resistance, and the super-hydrophobic property of the coating is reduced after an aging test, so that the antibacterial property is reduced.
Comparing example 1 with comparative example 6, it was found that comparative example 6 had excellent antibacterial properties but no hydrophobic and oleophobic properties. When the comparative example 6 was subjected to the aging test for 1000 hours, the antibacterial property of the coating was significantly deteriorated, mainly because the aging test performed ultraviolet irradiation and water mist spraying on the coating to simulate outdoor operation, and the comparative example 6 should not have excellent durability, so the aging test caused the antibacterial property to be deteriorated.
In conclusion, the embodiment has excellent super-hydrophobic, super-oleophobic, durable and antibacterial properties.
The above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention by this means. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (5)
1. The durable antibacterial antiviral super-amphiphobic coating is characterized by comprising a primer coated on the surface of a substrate and a finish paint attached to the primer, wherein the primer raw materials comprise fluorine-containing resin, acrylic resin, inorganic filler, a solvent A1 and an auxiliary agent, and the finish paint raw materials comprise super-hydrophobic super-oleophobic modified nano silicon dioxide, nano silver and a solvent A2;
the priming paint raw material comprises 20-30% of fluorine-containing resin, 10-15% of acrylic resin, 12-20% of inorganic filler, 20-30% of solvent and the balance of auxiliary agent by weight percentage;
the inorganic filler comprises 10 to 15 percent of 10 to 50 mu m inorganic filler B1 and 2 to 5 percent of 80 to 110 mu m inorganic filler B2 according to weight percentage;
the raw materials of the finish comprise 5-10% of nano silicon dioxide, 80-90% of absolute ethyl alcohol and the balance of nano silver, wherein the particle size of the nano silicon dioxide is 10-1000 nm, and the particle size of the nano silver is 20-100nm;
the preparation method of the antibacterial and antiviral super-amphiphobic coating comprises the following steps: uniformly mixing and dispersing the primer raw materials, spraying the mixture on the surface of a base material, and drying the surface of a primer coating after 5-30 min; uniformly mixing and dispersing the finish paint raw material, spraying the mixture on the primer paint, and curing at room temperature;
the fluorine-containing resin is fluorine-carbon resin.
2. The durable antibacterial antiviral super-amphiphobic coating of claim 1, wherein said inorganic filler B1 and inorganic filler B2 are both barium sulfate powder.
3. The durable antibacterial antiviral superamphiphobic coating of claim 1, wherein the solvent A1 is one or more of ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, ethanol.
4. The durable antibacterial antiviral superamphiphobic coating of claim 1, wherein the adjuvant is at least 3 of defoamer, co-solvent, dispersant, diluent.
5. The durable antibacterial antiviral super-amphiphobic coating of claim 1, wherein the super-hydrophobic super-oleophobic modified nano-silica is prepared by the following process: sequentially adding an alcohol solvent, a basic catalyst and silicate ester into a reactor according to the mass ratio of 30-50, namely, 0.1-2.0; adding fluorine-containing organic matter with the mass ratio of 0.1-1.0 into a reactor, and continuously reacting for 8 hours at the temperature of 50-70 ℃ to obtain super-hydrophobic and super-oleophobic SiO 2 And (3) nanoparticles.
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