CN114015265B - Long-acting antibacterial coating material and preparation method thereof - Google Patents

Long-acting antibacterial coating material and preparation method thereof Download PDF

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CN114015265B
CN114015265B CN202111273956.5A CN202111273956A CN114015265B CN 114015265 B CN114015265 B CN 114015265B CN 202111273956 A CN202111273956 A CN 202111273956A CN 114015265 B CN114015265 B CN 114015265B
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nano particles
iron oxide
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CN114015265A (en
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郑翔
叶德威
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Xiamen Fuyuan High Tech Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/02Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D129/00Coating 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2265Oxides; Hydroxides of metals of iron
    • C08K2003/2272Ferric oxide (Fe2O3)
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

Abstract

The invention discloses a coating material with long-acting antibiosis, which comprises the following raw materials: 100 parts of polyvinyl alcohol, 0.1-3 parts of ferric oxide micro-nano particles, 500-5000 parts of ultrapure water, 0.25-5 parts of organic antibacterial molecules, 0.1-2 parts of silanized quaternary ammonium salt and 0-3 parts of film forming additives; wherein the particle size of the iron oxide micro-nano particles is 50-1000 nm; the organic antibacterial molecules have coordination groups containing lone pair electrons, and the organic antibacterial molecules are contacted with the iron oxide micro-nano particles to form a coordination effect. The invention also discloses a preparation method of the composition. According to the invention, the long-acting antibacterial performance of the coating is improved through the interaction among the silanized quaternary ammonium salt, the iron oxide micro-nano particles and the organic antibacterial molecules.

Description

Long-acting antibacterial coating material and preparation method thereof
Technical Field
The invention relates to the technical field of antibacterial materials, in particular to a coating material with long-acting antibacterial property and a preparation method thereof.
Background
Microorganisms are organisms that are widely found in nature and include fungi, bacteria, viruses, and the like. These ubiquitous microscopic living bodies, invisible to the naked eye, represent the greatest potential hazards of human health and public safety. Some viruses survive on smooth surfaces for long periods of time and spread across the surface of various objects in the living environment, causing the rapid spread of infectious diseases.
As one of the main means for disinfecting the surface of the living environment, various disinfectants such as hypochlorous acid, hydrogen peroxide and the like are used for killing the surface in a whole space, and the method is the most commonly used surface disinfection means at present. In addition, alcohol is also used as a surface disinfectant for small objects. In addition, space sterilization using ultraviolet rays is also one of the commonly used sterilization means. However, disinfectants with strong oxidation such as hypochlorous acid and hydrogen peroxide and disinfectants with strong volatility such as alcohol have short action time and little residue, and can not realize the function of permanent killing although the disinfectants are quick, efficient and low-cost. And the disinfection and sterilization treatment by using ultraviolet rays is dangerous, and if the ultraviolet lamp is forgotten to be turned off in the daytime, the people in the environment can be greatly injured. Thus, there is currently no viable solution for long-term sterilization. However, in certain crowded places and areas, surfaces without long-lasting antimicrobial sterilization capability are easily and quickly become a route of transmission after disinfection. Therefore, a novel coating with bactericidal effect and long-acting bacteriostasis is developed, so that public health and safety are protected to the maximum extent, environmental pollution is reduced, and the coating has important economic value and significance.
PVA (polyvinyl alcohol) is used as a non-toxic and harmless film forming agent with good biocompatibility, and is widely applied to various industries, such as cosmetics, biomedicine, electronic components, filter materials and the like. The PVA monomer contains hydroxyl group and can form hydrogen bond with water, so that the PVA monomer is a high molecular polymer which can be dissolved in water, and great advantage is brought to the use of PVA. The PVA and the antibacterial component are mixed in the aqueous solution and then coated, so that an antibacterial film can be formed on the surface of the product. However, PVA has excellent water solubility and is easily dissolved or swelled by water during use, and the antibacterial film layer is easily and rapidly lost during actual use to cause failure. Therefore, how to balance the water solubility of PVA and the water solubility after film formation is a problem to be solved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a coating material with long-acting antibacterial property and a preparation method thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a coating material with long-acting antibiosis comprises the following raw materials in percentage by weight: 100 parts of polyvinyl alcohol, 500-5000 parts of ultrapure water, 0.1-3 parts of iron oxide micro-nano particles, 0.25-5 parts of organic antibacterial molecules, 0.1-2 parts of silanized quaternary ammonium salt and 0-3 parts of film forming additives; wherein the particle size of the iron oxide micro-nano particles is 50-1000 nm; the organic antibacterial molecules have coordination groups containing lone pair electrons, and the organic antibacterial molecules are contacted with the iron oxide micro-nano particles to form a coordination effect.
Optionally, the alcoholysis degree of the polyvinyl alcohol is 90-99.9%, and the polymerization degree is 1700-1900.
Optionally, the organic antimicrobial molecule comprises at least one of octenidine, polyhexamethylene biguanide, and polyhexamethylene guanidine.
Optionally, the weight ratio of the iron oxide micro-nano particles to the organic antibacterial molecules is 1:1 to 10.
Optionally, the particle size of the iron oxide micro-nano particles is 100-500 nm.
Optionally, the film-forming additive is a silane-based compound.
A preparation method of the coating material with long-acting antibiosis comprises the following steps:
1) According to the proportion, 100 parts by weight of polyvinyl alcohol is stirred and dissolved in 500-5000 parts by weight of ultrapure water with the temperature higher than 90 ℃, and then the ultrapure water is cooled to room temperature;
2) Adding 0.1-3 parts by weight of iron oxide micro-nano particles, and stirring to uniformly disperse the iron oxide micro-nano particles in the sol;
3) Adding 0.1-2 parts by weight of silanized quaternary ammonium salt, and fully stirring for dissolving;
4) Adding 0.25-5 parts by weight of organic antibacterial molecules, ultrasonically stirring for 12-36 hours, and mixing, wherein the organic antibacterial molecules are contacted with the iron oxide micro-nano particles to form a coordination effect;
5) Adding 0-3 parts by weight of film forming additive, uniformly mixing, coating on the surface of an object, and drying to form the long-acting antibacterial coating.
Optionally, the thickness of the coating is 0.1 to 10 microns.
Optionally, in the step 5), the coating is performed by spraying a single-fluid spray gun on the surface of the object, wherein the spraying amount is 0.05-0.5L/m 2
Optionally, in step 1), 100 parts by weight of polyvinyl alcohol is dissolved in 800 to 2000 parts by weight of ultrapure water having a temperature higher than 90 ℃ by stirring, and then cooled to room temperature.
The beneficial effects of the invention are as follows:
the silanized quaternary ammonium salt and PVA are subjected to dehydration condensation to form a net structure, so that the water resistance is improved, the coating film is prevented from being rapidly damaged in daily use, and the structure is more stable; on the other hand, the antibacterial performance of the PVA film brings long-acting antibacterial capability to the PVA film;
the iron oxide micro-nano particles are crosslinked with PVA and silanized quaternary ammonium salt, so that the water resistance is further improved; on the other hand, organic antibacterial molecules capable of coordinating with ferric oxide are introduced, so that the effect of fixing the organic antibacterial molecules in the PVA film is achieved, and the antibacterial performance of the film is improved;
the effect of combining antibiosis and sterilization is achieved through the interaction and combination of the components.
Detailed Description
The following specific examples further illustrate the invention.
A coating material with long-acting antibiosis comprises the following raw materials in percentage by weight: 100 parts of polyvinyl alcohol, 500-5000 parts of ultrapure water, 0.1-3 parts of iron oxide micro-nano particles, 0.25-5 parts of organic antibacterial molecules, 0.1-2 parts of silanized quaternary ammonium salt and 0-3 parts of film forming additives.
The alcoholysis degree of PVA is 90-99.9%, preferably 95-99.9%, and the polymerization degree is 1700-1900.
The particle size range of the iron oxide micro-nano particles is 50-1000 nm, preferably 100-500 nm. The ferric oxide micro-nano particles are mainly ferric oxide, wherein ferric ions account for more than 90% of the concentration of all ferric ions.
The organic antibacterial molecule should contain groups with related coordination ligands, such as oxygen lone pair (hydroxyl, sulfhydryl, etc.) and nitrogen lone pair (amine, amide, etc.). The coordination group contains lone pair electrons and can be matched with Fe with empty d electron orbitals 3+ The metal centers are coordinately bound. Organic antimicrobial molecules include, but are not limited to, otitidOne or more of nifedipine, polyhexamethylene biguanide, polyhexamethylene guanidine, and the like. As an important component of a new generation of broad-spectrum sterilization, organic antibacterial molecules can be combined with microbial cell membranes, cell walls and virus capsids with negative charges through intramolecular positive charge groups, so that the effect of broad-spectrum sterilization of bacteria and viruses is achieved. Because the action mechanism of the antibacterial agent is not specific to a certain biological process, the antibacterial agent cannot generate the drug resistance of bacteria to cause failure in the long-term use process through the organic antibacterial molecules with the positive charge groups.
In order to improve the adhesion strength of the formed antibacterial coating to the surface of the object, a film-forming additive may be added, and the film-forming additive may be a silane-based compound, such as silok 8333.
The preparation method of the coating material with long-acting antibiosis comprises the following steps:
1) According to the proportion, 100 parts by weight of polyvinyl alcohol is stirred and dissolved in 500-5000 parts by weight of ultrapure water with the temperature higher than 90 ℃, and then the ultrapure water is cooled to the room temperature; more preferably, the amount of ultrapure water is 500 to 2000 parts by weight;
2) Adding 0.1-3 parts by weight of iron oxide micro-nano particles, and stirring to uniformly disperse the iron oxide micro-nano particles in the sol;
3) Adding 0.1-2 parts by weight of silanized quaternary ammonium salt, and fully stirring for dissolving;
4) Adding 0.25-5 parts by weight of organic antibacterial molecules, ultrasonically stirring for 12-36 hours, and mixing, wherein the organic antibacterial molecules are contacted with the iron oxide micro-nano particles to form a coordination effect;
5) Adding 0-3 parts by weight of film-forming additive, uniformly mixing, coating on the surface of an object, and drying to form the long-acting antibacterial coating.
The coating layer may be formed by, but not limited to, dip coating, spin coating, spray coating, or other film forming methods. Among them, the spraying is simple to use, the film forming is rapid, and the method is not limited by the surface shape of the object and is the most ideal mode. The spraying process adopted by the invention is to spray a single-fluid spray gun on the surface of an object, and the spraying amount is 0.05-0.5L/m 2 . Thereby forming a coating on the surface of the object. Thickness of coatingThe degree is about 0.1 to 10 microns.
In the process of spraying, curing and film forming of the spray, silicon oxygen bonds of the silanized quaternary ammonium salt are hydrolyzed and condensed with hydroxyl groups of PVA molecular chains, so that the PVA chains are driven to form a net structure, the crosslinking degree among the PVA high molecular chains is improved, on one hand, the antibacterial capability is brought to the PVA film, on the other hand, the water resistance is increased, and the generated coating film is prevented from being rapidly damaged in daily use; meanwhile, hydroxyl generated on the surface of the iron oxide micro-nano particles can be subjected to crosslinking or dehydration condensation with hydroxyl groups of a PVA chain and silicon-oxygen bonds of a crosslinking antibacterial agent, so that the water resistance of the PVA film is further improved, on the other hand, ferric ions on the surface of the iron oxide nano particles can generate a coordination effect with organic antibacterial molecules, and the antibacterial capability of the PVA antibacterial layer can be effectively improved by introducing the organic antibacterial molecules. Wherein the weight ratio of the ferric oxide micro-nano particles to the organic antibacterial molecules is 1: (1-10).
Therefore, the introduction of the organic silicon quaternary ammonium salt and the organic antibacterial molecules can provide antibacterial capability for the spray coating. The ferric oxide micro-nano particles and the organic silicon quaternary ammonium salt can adjust the water resistance of the PVA layer and improve the long-acting property of the coating. The nano iron oxide can anchor antibacterial molecules in the PVA layer, and the antibacterial efficiency and the durability are maximized. The film forming additive can improve the adhesion strength of the coating film and improve the firmness of the coating film. In addition, the quaternary ammonium silicone salts can also provide better surface adhesion and increase durability. The obtained coating has stronger stability and can keep the antibacterial performance for a long time.
In the examples disclosed below, quaternary silicone salt PC-9911 was obtained from Sesbania silicone; octenidine hydrochloride was purchased from wuhananabai chemical; the rest chemical reagents are general commercial products.
Example 1
For 100 parts by weight of polyvinyl alcohol, 1000 parts by weight of 18 megaohm ultrapure water is heated to 90 ℃ or higher, polyvinyl alcohol (alcoholysis degree is about 90%, polymerization degree is about 1800) is dissolved in the ultrapure water with stirring, the temperature is maintained, stirring is carried out for 2 hours until the polyvinyl alcohol is uniform, and cooling is carried out to room temperature. Then, 1 weight part of iron oxide micro-nano particles (20-200 n) are addedm), stirring for 1 hour and uniformly mixing. Subsequently, 2 parts by weight of PC-9911, an antibacterial crosslinking agent, was added to the mixture, and the mixture was sufficiently stirred for 10min to dissolve. And then, adding 1 part by weight of octenidine hydrochloride, and dissolving by ultrasonic for 12-36 hours to obtain a mixed solution. The mixed solution is evenly shaken before spraying, and then the mixed solution is coated on the surface of a plastic culture dish by a single-fluid spray gun, wherein the spraying density is about 0.1L/m 2 And naturally drying to form the long-acting antibacterial coating, wherein the thickness of the coating is about 10 mu m.
Example 2
For 100 parts by weight of polyvinyl alcohol, 1500 parts by weight of 18 megaohm ultrapure water is heated to 90 ℃ or higher, polyvinyl alcohol (alcoholysis degree is about 90%, polymerization degree is about 1800) is dissolved in the ultrapure water with stirring, the temperature is maintained, stirring is carried out for 2 hours until the polyvinyl alcohol is uniform, and cooling is carried out to room temperature. Subsequently, 1 part by weight of iron oxide nanoparticles (20 to 200 nm) were added, stirred for 1 hour, and mixed uniformly. Subsequently, 2 parts by weight of PC-9911, an antibacterial crosslinking agent, was added to the mixture, and the mixture was sufficiently stirred for 10min to dissolve. And then, adding 1.5 parts by weight of octenidine hydrochloride, and dissolving by ultrasonic for 12-36 hours to obtain a mixed solution. The mixed solution is evenly shaken before spraying, and then the mixed solution is coated on the surface of a plastic culture dish by a single-fluid spray gun, wherein the spraying density is about 0.1L/m 2 And naturally drying to form the long-acting antibacterial coating, wherein the thickness of the coating is about 10 mu m.
Comparative example 1
For 100 parts by weight of polyvinyl alcohol, 1000 parts by weight of 18 megaohm ultrapure water was heated to 90 ℃ or higher, polyvinyl alcohol (alcoholysis degree of about 90%, polymerization degree of about 1800) was dissolved in the ultrapure water with stirring, the temperature was maintained, stirring was carried out for 2 hours until homogeneity was reached, and cooling was carried out to room temperature. The mixed solution is evenly shaken before spraying, and then the mixed solution is coated on the surface of a plastic culture dish by a single-fluid spray gun, wherein the spraying density is about 0.1L/m 2 And naturally dried to a coating thickness of about 10 μm.
Comparative example 2
For 100 parts by weight of polyvinyl alcohol, 1000 parts by weight of ultrapure water of 18 megaohms is heated to 90 ℃ or higher, polyvinyl alcohol (degree of alcoholysis is about 90%, degree of polymerization is about 1800) is dissolved in the ultrapure water with stirring,the temperature was maintained for 2 hours with stirring until homogeneous and cooled to room temperature. And then, adding 1 part by weight of octenidine hydrochloride, and dissolving by ultrasonic for 12-36 hours to obtain a mixed solution. Shaking before spraying, coating the mixed solution on the surface of a plastic culture dish by using a single-fluid spray gun, and naturally drying to obtain a spray density of about 0.1L/m 2 The coating thickness was about 10 μm.
To verify the long-term efficacy, we soaked example 1, comparative example 1 and comparative example 2 in ultrapure water for 24h and performed a surface antimicrobial test.
The antibacterial test method comprises the following steps:
3ml of staphylococcus aureus liquid is dripped on the surface of the culture dish sprayed with the PVA antibacterial layer, and the culture dish is incubated for 24 times. Shaking up, sucking 100 microliter of the bacterial liquid into a 96-well plate, and measuring the OD value. The results are as follows:
Figure BDA0003328757100000061
it can be seen that the examples all showed excellent antibacterial ability. Comparative example 1 had no antibacterial ability since no antibacterial component was added. Comparative example 2 also shows antibacterial ability due to the addition of octenidine organic antibacterial molecule. However, after 24 hours of soaking, since comparative example 2 was not treated to make any PVA water-resistant and, at the same time, octenidine was not anchored in the PVA layer by iron oxide, the soaked comparative example 2 lost the antibacterial ability, and, correspondingly, example 1 after 24 hours of soaking still maintained good antibacterial ability.
The above examples are only intended to further illustrate the long-lasting antibacterial coating material and the preparation method thereof, but the present invention is not limited to the examples, and any simple modifications, equivalent changes and modifications made to the above examples according to the technical essence of the present invention fall within the scope of the technical solution of the present invention.

Claims (9)

1. A coating material with long-acting antibacterial property is characterized in that the coating material comprises the following raw materials in proportion: 100 parts of polyvinyl alcohol, 500-5000 parts of ultrapure water, 0.1-3 parts of iron oxide micro-nano particles, 0.25-5 parts of organic antibacterial molecules, 0.1-2 parts of silanized quaternary ammonium salt and 0-3 parts of film forming additive; wherein the particle size of the iron oxide micro-nano particles is 50-1000 nm; the organic antibacterial molecules are octenidine, the organic antibacterial molecules are in contact with the iron oxide micro-nano particles to form a coordination effect, and the iron oxide micro-nano particles anchor the organic antibacterial molecules in the coating.
2. The coating material having a long-lasting antibacterial property according to claim 1, characterized in that: the alcoholysis degree of the polyvinyl alcohol is 90-99.9%, and the polymerization degree is 1700-1900.
3. The coating material having a long-lasting antibacterial property according to claim 1, characterized in that: the weight ratio of the iron oxide micro-nano particles to the organic antibacterial molecules is 1:1 to 10.
4. The coating material having a long-lasting antibacterial property according to claim 1, characterized in that: the particle size of the iron oxide micro-nano particles is 100-500 nm.
5. The coating material having a long-lasting antibacterial property according to claim 1, characterized in that: the film-forming additive is a silane compound.
6. A method for preparing a coating material with long-lasting antibacterial property according to any one of claims 1 to 5, comprising the steps of:
1) According to the proportion, 100 parts by weight of polyvinyl alcohol is stirred and dissolved in 500-5000 parts by weight of ultrapure water with the temperature higher than 90 ℃, and then the ultrapure water is cooled to room temperature;
2) Adding 0.1-3 parts by weight of iron oxide micro-nano particles, and stirring to uniformly disperse the iron oxide micro-nano particles in the sol;
3) Adding 0.1-2 parts by weight of silanized quaternary ammonium salt, and fully stirring for dissolving;
4) Adding 0.25-5 parts by weight of organic antibacterial molecules, ultrasonically stirring for 12-36 hours, and mixing, wherein the organic antibacterial molecules are contacted with the iron oxide micro-nano particles to form a coordination effect;
5) Adding 0-3 parts by weight of film-forming additive, uniformly mixing, coating on the surface of an object, and drying to form the long-acting antibacterial coating.
7. The method of claim 6, wherein: the thickness of the coating is 0.1-10 microns.
8. The method of claim 6, wherein: in the step 5), the coating is carried out by adopting a single-fluid spray gun to spray on the surface of the object, and the spraying amount is 0.05-0.5L/m 2
9. The method of claim 6, wherein: in the step 1), 100 parts by weight of polyvinyl alcohol is dissolved in 800 to 2000 parts by weight of ultrapure water with a temperature higher than 90 ℃ by stirring, and then the solution is cooled to room temperature.
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