CN114276732A - Antibacterial and anticorrosive paint and coating based on silver-doped quaternary ammonium-based nano silica sol and epoxy fluorine-containing acrylate resin - Google Patents
Antibacterial and anticorrosive paint and coating based on silver-doped quaternary ammonium-based nano silica sol and epoxy fluorine-containing acrylate resin Download PDFInfo
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Abstract
The invention discloses an antibacterial and anticorrosive paint and a coating based on silver-doped quaternary ammonium-based nano silica sol and epoxy fluorine-containing acrylate resin. The epoxy fluorine-containing acrylate resin is used as a water-repellent and oil-repellent film-forming substance, the nano silver coated by the quaternary ammonium silicon sol is used as a sterilization component, and the nano silver is compounded with a nano pigment filler, an organic amine curing agent and the like, so that the prepared coating can not only overcome the problems of sedimentation and layering easily caused by inorganic nano silver when meeting organic fluorine resin, but also can be used for preparing a coating, the contact angle of water can reach 110.1-148.2 degrees, the antibacterial rate of the coating on staphylococcus aureus can reach more than 99 percent, the antibacterial rate on escherichia coli can reach more than 99 percent, and good waterproof, antifouling, antibacterial and anticorrosion effects are shown.
Description
Technical Field
The invention belongs to the field of functional resin and coating, and relates to an antibacterial anticorrosive coating and a coating prepared based on silver-doped quaternary ammonium based nano silica sol and epoxy fluorine-containing acrylate resin.
Background
The fluorine-containing acrylate resin has low surface energy, good film-forming property and excellent water and oil repellency, and a functional coating prepared by combining the fluorine-containing acrylate resin with nano pigment and filler (see US5705276, CN1222929, CN101508755, WO2009/126467, US6126849, US5242487 and US2001/0020077) is widely applied to the aspects of household appliance and wind power antifouling coatings, packaging moisture-proof and anti-freezing coatings of electronic and electrical elements, antibacterial and anti-corrosion inner coatings of fuel oil storage and transportation equipment and the like.
The traditional fluorine-containing acrylate resin-based coating mainly adopts hydroxyl fluorine-containing polyacrylate resin as a film-forming substance, and isocyanate substances such as N3390, N75 and the like are mostly adopted as a curing agent. Epoxy functional groups are introduced into the fluorine-containing polyacrylate structure, so that epoxy modified fluorinated polyacrylate resin can be prepared, the curing mode of the organic fluororesin can be expanded to the ring-opening reaction of the epoxy groups caused by curing agents such as polyamine, acid anhydride and the like, and a coating with novel structure and performance are expected to be obtained.
Super-hydrophobic research shows that under the condition that a layer of hydrophobic substance exists on the surface of the base material, the roughness of the surface of the base material is increased, the contact angle of water on the surface of the base material is increased, the rolling angle is reduced, and the water and oil repellent effect of the coating (film) can be improved. Therefore, the combination of the nano-micron coarse structure and the fluororesin is a common strategy for constructing a super-hydrophobic and oleophobic coating (film), improving the flame retardance of the coating (film) and increasing the hardness. However, in the research, inorganic nano silver, CuO/Cu are found2O、ZnO and the like are directly added into a fluororesin system as a coarse component, although the hydrophobicity of the coating is increased and the coating can be endowed with the functions of sterilization and bacteriostasis, the inorganic components such as unmodified nano silver and the like are easily precipitated and layered due to poor mutual solubility of the inorganic components and organic components after being directly added into the hydrophobic fluororesin system, so that the using effect of the coating (film) is influenced.
Disclosure of Invention
The invention aims to provide an antibacterial anticorrosive paint and a coating based on silver-hybrid quaternary ammonium-based nano silica sol and epoxy fluorine-containing acrylate resin. The inorganic nano silver is coated and chemically modified by using the long-chain bactericidal quaternary ammonium group modified silica sol, so that the problems of sedimentation and layering of the nano silver in organic fluororesin are solved, and the silver-mixed fluororesin antibacterial anticorrosive paint and coating which are uniformly dispersed and have excellent performance are obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
an antibacterial and anticorrosive coating of silver-doped fluororesin, which comprises epoxy fluorine-containing acrylate resin (EFA) as a component of a water-and oil-repellent film-forming substance and silver-doped quaternary ammonium-based nano silica sol as a component of a bactericide and dispersed in the epoxy fluorine-containing acrylate resin; the silver hybrid quaternary ammonium base nano silica sol is nano silver (QAg-SiO) coated by quaternary ammonium silica sol2)。
Preferably, the antibacterial and anticorrosive paint consists of paint A and paint B; the paint A consists of 100 parts of epoxy fluorine-containing acrylate resin, 5-25 parts of quaternary ammonium silicon sol-coated nano silver, 0-25 parts of hydrophobic nano pigment filler, 0.1-1.0 part of wetting dispersant and 10-30 parts of paint solvent by mass; the paint B is an organic amine curing agent, and the quantity ratio of epoxy groups in the epoxy fluorine-containing acrylate resin contained in the paint A to N-H bonds in the paint B is 1: 1-1.1.
Preferably, the main component of the epoxy fluorine-containing acrylate resin is selected from one or more of multipolymers with the structures shown as formula (1) and formula (2):
wherein n, m, x, y are integers of 0 or more (e.g., 0,1,2,3 …); rfC selected from the group consisting of perfluorooctylethyl group, perfluorohexylethyl group, dodecafluoroheptyl group, hexafluorobutyl group, perfluoropolyether group and the like4-C14One or more of the fluoroalkyl groups of (a); r is C1-C18One of the alkyl groups of (1)(e.g., -CH)3、-C18H37Etc.); m, M 'and M' are H or CH3；
a. b is any one of integers from 0 to 10 (e.g., 0,1,2,3 …), and 10 ≧ a + b > 0.
Preferably, the main component of the epoxy fluorine-containing acrylate resin is selected from C4-14Fluoroalkyl (meth) acrylate (FA) -co-alkenyl epoxy compound (AE) copolymer, C4-14Fluoroalkyl (meth) acrylates (FA) -co-C1-18Alkyl (meth) acrylate (RA) -co-alkenyl epoxy Compound (AE) copolymer, C4-14Fluoroalkyl (meth) acrylate (FA) -co-Styrene (ST) -co-alkenyl epoxy compound (AE) copolymer, C4-14Fluoroalkyl (meth) acrylates (FA) -co-C1-18One or more of alkyl (meth) acrylate (RA) -Styrene (ST) -co-alkenyl epoxy compound (AE) copolymers; the solid content of the epoxy fluorine-containing acrylate resin is 50-60%, the viscosity is 500-1500mPa.s, the epoxy group content (calculated by the mole number of the epoxy group contained in each 100g of the copolymer) is 0.09-0.2%, and the fluorine monomer content (calculated by the mass fraction of the fluorine monomer in the copolymer) is 40-86%.
Preferably, C in the epoxy fluorine-containing acrylate resin chain unit4-14The fluoroalkyl (meth) acrylate (FA) is selected from perfluorooctylethyl (meth) acrylate [ heptadecafluorodecyl (meth) acrylate, 1H,2H, 2H-heptadecafluorodecyl methacrylate, 1,2, 2-tetrahydroperfluorodecyl methacrylate]Perfluorohexylethyl (meth) acrylate [ also known as tridecafluorooctyl (meth) acrylate, 1H,2H, 2H-perfluorooctyl methacrylate]One or more of dodecafluoroheptyl (meth) acrylate, hexafluorobutyl (meth) acrylate, and perfluoropolyether (meth) acrylate having Mn ═ 1000-; c1-18The alkyl (meth) acrylate (RA) is selected from methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate [ including (meth) acrylic acidN-octyl ester of acid and isooctyl (meth) acrylate]One or two of (meth) acrylic acid dodecyl ester, (meth) acrylic acid cetyl ester, (meth) acrylic acid stearyl ester, (meth) acrylic acid cyclohexyl ester and (meth) acrylic acid isobornyl ester, and C1-18The alkyl (meth) acrylates (RA) preferably contain C from them4-18Alkyl aliphatic and alicyclic (meth) acrylates; the alkenyl epoxy compound (AE) is one selected from allyl glycidyl ether, glycidyl (meth) acrylate, allyl polyoxyethylene epoxy ether, and allyl polyoxypropylene epoxy ether.
Preferably, said C4-14The fluoroalkyl (meth) acrylate (FA) -co-alkenyl epoxy compound (AE) copolymer is selected from the group consisting of perfluorooctylethyl (meth) acrylate-co-allyl glycidyl ether, perfluorohexylethyl (meth) acrylate-co-allyl glycidyl ether, dodecafluoroheptyl (meth) acrylate-co-allyl glycidyl ether, perfluorooctylethyl (meth) acrylate-co-hexafluorobutyl (meth) acrylate-co-allyl glycidyl ether [ also known as heptadecafluorodecyl (meth) acrylate-co-hexafluorobutyl (meth) acrylate-co-allyl glycidyl ether]Perfluorohexylethyl (meth) acrylate-co- (meth) acrylate hexafluorobutyl-co-allyl glycidyl ether, (meth) dodecafluoroheptyl acrylate-co- (meth) acrylate hexafluorobutyl-co-allyl glycidyl ether, perfluorooctylethyl (meth) acrylate-co-perfluoropolyether acrylate-co- (meth) acrylate hexafluorobutyl-co-allyl glycidyl ether, perfluorohexylethyl (meth) acrylate-co-perfluoropolyether acrylate hexafluorobutyl-co-allyl glycidyl ether, (meth) dodecafluoroheptyl acrylate-co-perfluoropolyether acrylate-co- (meth) acrylate hexafluorobutyl-co-allyl glycidyl ether, and the like.
Preferably, said C4-14Fluoroalkyl (meth) acrylates (FA) -co-C1-18The alkyl (meth) acrylate (RA) -co-alkenyl epoxy compound (AE) copolymer is selected from perfluorooctylethyl (meth) acrylate-co- (stearyl (meth) acrylate-co-allyl glycidyl ether, perfluorohexylethyl (meth) acrylate-coOctadecyl (meth) acrylate-co-allyl glycidyl ether, dodecafluoroheptyl methacrylate-co-octadecyl (meth) acrylate-co-allyl glycidyl ether, perfluorooctylethyl (meth) acrylate-co-octadecyl (meth) acrylate-co-butyl (meth) acrylate-co-allyl glycidyl ether, perfluorohexylethyl (meth) acrylate-co-octadecyl (meth) acrylate-co-butyl (meth) acrylate-co-allyl glycidyl ether, perfluorooctylethyl (meth) acrylate-co-cyclohexyl (meth) acrylate-co-butyl (meth) acrylate-co-allyl glycidyl ether, perfluorooctyl ethyl (meth) acrylate, perfluorooctyl (meth) acrylate, and mixtures thereof, Perfluorohexylethyl (meth) acrylate-co- (cyclohexyl (meth) acrylate-co- (butyl (meth) acrylate-co-allyl glycidyl ether, dodecafluoroheptyl methacrylate-co- (cyclohexyl (meth) acrylate-co- (butyl (meth) acrylate-co-allyl glycidyl ether, perfluorooctylethyl (meth) acrylate-co- (stearyl (meth) acrylate-co- (butyl (meth) acrylate-co- (glycidyl (meth) acrylate), perfluorohexylethyl (meth) acrylate-co- (stearyl (meth) acrylate-co- (butyl (meth) acrylate-co- (glycidyl (meth) acrylate), Dodecafluoroheptyl methacrylate-co- (octadecyl (meth) acrylate-co- (butyl (meth) acrylate-co- (glycidyl (meth) acrylate), dodecafluoroheptyl methacrylate-co-hexafluorobutyl methacrylate-co- (octadecyl (meth) acrylate-co-butyl acrylate-co- (glycidyl (meth) acrylate), perfluorooctylethyl (meth) acrylate-co- (cyclohexyl (meth) acrylate-co- (butyl (meth) acrylate-co-glycidyl acrylate, perfluorohexylethyl (meth) acrylate-co- (cyclohexyl (meth) acrylate-co-glycidyl acrylate, dodecafluoroheptyl methacrylate-co- (cyclohexyl (meth) acrylate-co-glycidyl acrylate Glyceryl esters, perfluorohexylethyl (meth) acrylate-co-hexafluorobutyl methacrylate-co-stearyl (meth) acrylate-co-cyclohexyl (meth) acrylate-co-glycidyl acrylate, perfluorooctylethyl (meth) acrylate-co-perfluoropolyether (meth) acrylate-co-stearyl (meth) acrylate-co-allyl glycidyl ether, perfluorohexylethyl (meth) acrylate-co-perfluoropolyether (meth) acrylate-co- (meth) acrylateOctadecyl ester-co-allyl glycidyl ether, dodecafluoroheptyl (meth) acrylate-co-perfluoropolyether (meth) acrylate-co-octadecyl (meth) acrylate-co-allyl glycidyl ether, perfluorooctylethyl (meth) acrylate-co-perfluoropolyether (meth) acrylate-co-lauryl (meth) acrylate-co-allyl glycidyl ether, perfluorohexylethyl (meth) acrylate-co-perfluoropolyether (meth) acrylate-co-lauryl (meth) acrylate-co-allyl glycidyl ether, dodecafluoroheptyl (meth) acrylate-co-perfluoropolyether (meth) acrylate-co-lauryl (meth) acrylate-co-allyl glycidyl ether, and mixtures thereof, Perfluorooctylethyl (meth) acrylate-co-perfluoropolyether (meth) acrylate-co- (butyl (meth) acrylate-co-allyl glycidyl ether, perfluorohexylethyl (meth) acrylate-co-perfluoropolyether (meth) acrylate-co- (butyl (meth) acrylate-co-allyl glycidyl ether, dodecafluoroheptyl (meth) acrylate-co-perfluoropolyether (meth) acrylate-co- (butyl (meth) acrylate-co-allyl glycidyl ether, perfluorooctylethyl (meth) acrylate-co-perfluoropolyether (meth) acrylate-co- (cyclohexyl (meth) acrylate-co-allyl glycidyl ether, perfluorooctyl (meth) acrylate-co-perfluoropolyether (meth) acrylate, perfluorooctyl (meth) acrylate-co-allyl glycidyl ether, perfluorooctyl (meth) acrylate-co-allyl ether, perfluorooctyl (meth) acrylate-co-glycidyl ether, perfluorooctyl (meth) acrylate, and mixtures thereof, Perfluorohexylethyl (meth) acrylate-co-perfluoropolyether (meth) acrylate-co- (cyclohexyl (meth) acrylate-co-allyl glycidyl ether, dodecafluoroheptyl (meth) acrylate-co-perfluoropolyether (meth) acrylate-co- (cyclohexyl (meth) acrylate-co-allyl glycidyl ether, one of dodecafluoroheptyl (meth) acrylate-co- (hexafluorobutyl (meth) acrylate-co- (cyclohexyl (meth) acrylate-co-glycidyl acrylate), perfluorohexylethyl (meth) acrylate-co-perfluoropolyether (meth) acrylate-co- (dodecyl (meth) acrylate-co-allyl polyoxypropylene epoxy ether, and the like.
Preferably, said C4-14The fluoroalkyl (meth) acrylate (FA) -co-Styrene (ST) -co-Alkenyl Epoxy (AE) copolymer is selected from the group consisting of perfluorooctylethyl (meth) acrylate/perfluorohexylethyl (meth) acrylate/dodecafluoroheptyl methacrylate-co-styrene-co-allyl glycidyl ether (i.e., perfluorooctylethyl (meth) acrylate-co-styrene-co-allyl glycidyl ether)Glycerol ether, perfluorohexylethyl (meth) acrylate-co-styrene-co-allyl glycidyl ether, dodecafluoroheptyl methacrylate-co-styrene-co-allyl glycidyl ether), perfluorooctylethyl (meth) acrylate/perfluorohexylethyl (meth) acrylate/dodecafluoroheptyl methacrylate-co-styrene-co-allyl glycidyl ester, perfluorooctylethyl (meth) acrylate/perfluorohexylethyl (meth) acrylate/dodecafluoroheptyl methacrylate-co-styrene-co-allylpolyoxyethylene polyoxypropylene ether epoxy ether, and the like.
Preferably, said C4-14Fluoroalkyl (meth) acrylates (FA) -co-C1-18The alkyl (meth) acrylate (RA) -Styrene (ST) -co-Alkenyl Epoxy (AE) copolymer is selected from the group consisting of perfluorooctylethyl (meth) acrylate/perfluorohexylethyl (meth) acrylate/dodecafluoroheptyl methacrylate-co- (meth) acrylate C4-18Alcohol ester-co-styrene-co-allyl glycidyl ether, perfluorooctylethyl (meth) acrylate/perfluorohexylethyl (meth) acrylate/dodecafluoroheptyl methacrylate-co- (meth) acrylic acid C4-18Alcohol ester-co-styrene-co-allyl glycidyl ester, perfluorooctylethyl (meth) acrylate/perfluorohexylethyl (meth) acrylate/dodecafluoroheptyl methacrylate-co- (meth) acrylic acid C4-18Alcohol ester-co-styrene-co-allyl polyoxyethylene polyoxypropylene ether epoxy ether, perfluorohexylethyl (meth) acrylate-co-perfluoropolyether (meth) acrylate-co- (meth) acrylic acid C4-18Alcohol ester-co-allyl glycidyl ether, etc.
Preferably, the paint solvent is a substance which is mutually soluble with components such as epoxy fluorine-containing acrylate resin, quaternary ammonium silica sol coated nano silver and the like and is volatile after being heated, mainly comprises at least one of ester, ketone, alcohol ether, ether ester and the like, and preferably selects one or a mixture of any two of Ethyl Acetate (EA), Butyl Acetate (BA), propylene glycol dimethyl ether (PDM), acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), ethylene glycol methyl ether acetate (EMA), propylene glycol methyl ether acetate (PMA) and the like.
Preferably, the hydrophobicityThe nano pigment and filler is nano TiO2、ZnO, hydrophobic Al2O3Hydrophobic Al (OH)3Calcium carbonate, barium sulfate, etc.; the wetting dispersant is BYK-ATU or BYK-161 from BYK.
Preferably, the organic amine curing agent is at least one of organic amines having 2 to 3 amino groups in a molecule (mainly including aliphatic diamine, alicyclic diamine, polyamine, polyether amine, and the like), and preferably one or a mixture of any two of ethylenediamine, diethylenetriamine, isophoronediamine, 4 '-diaminodicyclohexylmethane, 4' -diaminodiphenylmethane, polyetheramine D230[ Mn (average molecular weight) ═ 230], polyetheramine D400(Mn ═ 400), polyetheramine ED600(Mn ═ 600), polyetheramine ED900(Mn ═ 900), polyetheramine D2000(Mn ═ 2000), and polyethertriamine T403(Mn ═ 400).
Preferably, the epoxy fluorine-containing acrylate resin can be prepared by the method of reference (for example, CN103937357) and by C4-14Fluoroalkyl (meth) acrylates (FA) and C1-18Alkyl (meth) acrylates (RA) and alkenyl epoxy compounds (AE) or C4-14Fluoroalkyl (meth) acrylates (FA) and C1-18Alkyl (methyl) acrylate (RA), Styrene (ST), alkenyl epoxy compound (AE) and the like, the copolymerization reaction temperature is 80-90 ℃, the reaction time is 2-4h, the solvent used in the polymerization reaction is Butyl Acetate (BA)/methyl isobutyl ketone (MIBK) mixed solvent (BA: MIBK 1:1-2, wt/wt), and the initiator is Benzoyl Peroxide (BPO) or Azobisisobutyronitrile (AIBN).
Preferably, the nano silver coated by the quaternary ammonium silica sol, namely the nano silver coated by the silica sol co-modified by the long-chain quaternary ammonium group and the long-chain alkyl group, is prepared by co-hydrolyzing and polycondensing components such as nano silver (Ag), quaternary ammonium silane (QSi), long-chain alkyl silane (RSi), Tetraethoxysilane (TEOS) and the like.
Preferably, the preparation method of the quaternary ammonium silicasol-coated nano silver specifically comprises the following steps: 1 part of nano silver, 5-10 parts of quaternary ammonium silane, 0-10 parts (for example, 5-10 parts) of long-chain alkyl silane and 10-20 parts of ethyl orthosilicate are dissolved in alcohol solvent by massStirring and uniformly mixing, performing ultrasonic dispersion at 25-30 ℃ for 30-60min, heating the ultrasonically dispersed system to 45-50 ℃, adjusting the pH of the system to 3-4, adding deionized water accounting for 5-15% of the total mass of QSi, RSi and TEOS into the system, performing hydrolytic polycondensation reaction to obtain a transparent-slightly turbid liquid product, recovering an alcohol solvent from the product under reduced pressure, removing low-boiling-point substances in the product, and performing vacuum drying to obtain nano silver coated by quaternary ammonium silicasol, wherein the label is QAg-SiO2。
Preferably, the quaternary ammonium silicasol coated nano silver (QAg-SiO)2) In the preparation method, the quaternary ammonium silane has the solid content of 40-60 percent, and the effective component (molecule) contains C8-18Alkyl long chain organosilicon quaternary ammonium salt bactericide, such as U.S. Dow Corning company DC-5700[ effective component is (trimethoxysilylpropyl) octadecyl dimethyl ammonium chloride)]Or the effective component is [3- (trimethoxysilylpropyl) -2-hydroxy-oxypropyl]A long-chain organosilicon quaternary ammonium salt bactericide of octadecyl dimethyl acetate quaternary ammonium salt; the long-chain alkyl silane is selected from n-octyl trimethoxy silane, n-octyl triethoxy silane, n-dodecyl trimethoxy silane, n-dodecyl triethoxy silane, n-hexadecyl trimethoxy silane, n-hexadecyl triethoxy silane, n-octadecyl trimethoxy silane, n-octadecyl triethoxy silane and the like, and the molecular of the long-chain alkyl silane contains C8-18One of alkyl trialkoxysilanes (and preferably n-octyltrimethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane) which are liquid at room temperature; the alcohol solvent is one of micromolecular alcohols such as methanol, ethanol, isopropanol and the like, and the dosage of the solvent is 100-200% of the total mass of the nano Ag, QSi, RSi and TEOS; the reaction temperature of the hydrolysis polycondensation reaction of the nano Ag and QSi, RSi and TEOS is 40-50 ℃, and the reaction time is 24-48 h.
The preparation method of the silver-doped fluororesin antibacterial anticorrosive paint comprises the following steps:
1) preparation of paint A: mixing the weighed epoxy fluorine-containing acrylate resin, the nano silver coated by the quaternary ammonium silicasol, the hydrophobic nano pigment and filler, the wetting dispersant and the paint solvent, and then adding the mixture into a reactor at the temperature of 1000-1500rStirring and dispersing for 30-60min at min, and vacuum degassing for 10-15min (P)Watch (A)About 0.3 to about 0.6 MPa; the air bubbles wrapped in the resin are broken through decompression, and the gas is discharged out of the resin system) to obtain a mixture, namely paint A;
2) preparation of paint B: weighing the organic amine curing agent according to the weight ratio of epoxy groups in the epoxy fluorine-containing acrylate resin in the paint A to N-H bond substances in the organic amine curing agent of 1:1-1.1, thus obtaining paint B;
3) mixing paint A and paint B.
The antibacterial and anticorrosive coating is prepared on a base material by diluting, coating and curing the antibacterial and anticorrosive coating of the silver-doped fluororesin.
Preferably, the substrate is selected from a metal substrate (such as tinplate, stainless steel, steel plate, aluminum alloy, etc.) or a non-metal substrate (such as glass, ceramic, floor tile, etc.) after sand blasting or roughening treatment.
Preferably, the dilution specifically comprises the following steps: the silver-doped fluororesin antibacterial anticorrosive paint is prepared by adopting a Butyl Acetate (BA)/methyl isobutyl ketone (MIBK) mixed solvent (BA: MIBK ═ 1:1-2, wt/wt) to adjust the solid content to 30% -45%.
Preferably, the silver-doped fluororesin antibacterial and anticorrosive paint is coated on a coating (with the thickness of 25-30 μm) formed by a primer on the surface of a base material by adopting one of spraying, brushing, rolling, bar coating and the like, and also can be directly coated on the surface of a clean metal or nonmetal after sand blasting or roughening treatment.
Preferably, the curing conditions are as follows: the silver-mixed fluororesin antibacterial anticorrosive paint coated on the base material is dried for 20-30min at the temperature of 120-150 ℃ after leveling and surface drying.
The invention has the beneficial effects that:
the fluorine-containing antibacterial anticorrosive coating is compounded by the components of nano silver coated by quaternary ammonium silicasol, low surface energy hydrophobic and oleophobic epoxy fluorine-containing acrylate resin and the like, can improve the compatibility of the nano silver and an organic phase, solve the problem of easy sedimentation and delamination of inorganic metals when meeting the organic phase, and effectively play the water and oil repellent effect of fluorocarbon groups through a coating formed by curing organic amine so that the coating has good antibacterial, anticorrosive and moisture-proof effects (the antibacterial rate of the coating on staphylococcus aureus can reach more than 99 percent, the antibacterial rate on escherichia coli can reach more than 99 percent, and the contact angle WCA of water on the surface of the coating can reach 110.1-148.2 degrees).
Furthermore, the invention blends, ultrasonically disperses and hydrolyzes nano-silver, long-chain quaternary ammonium silane (such as DC-5700) with surface activity and dispersion effect, lipophilic long-chain alkyl trimethoxy silane, ethyl orthosilicate and the like in alcohol solvent for copolycondensation, thereby enabling bactericidal long-chain quaternary ammonium group and lipophilic long-chain alkyl to be polycondensed and chemically combined on the surface of nano-silver particles, and obtaining QAg-SiO2Not only the dispersion stability is improved (compared with nano Ag), but also the sterilization and bacteriostasis effects of the long-chain organic quaternary ammonium salt and the nano Ag (the advantages and the performances of the inorganic-organic hybrid bactericide are integrated) can be considered, and a good sterilization effect is shown.
Drawings
FIG. 1 is QAg-SiO2Infrared (IR) spectrum of (a).
Fig. 2 is the appearance of uncoated nano silver powder.
FIG. 3 is QAg-SiO2The appearance of (d) and the particle size distribution of the liquid phase.
FIG. 4 shows QAg-SiO2Transmission Electron Microscope (TEM) photograph of (coated nano silver in the inner dotted circle).
Detailed Description
The present invention is further illustrated by the following examples, which are provided only for the purpose of illustration and are not intended to limit the scope of the present invention.
Aiming at the problem that the commercially available nano silver powder is easy to settle and delaminate when meeting organic fluorine resin, the invention utilizes a sol-gel method to carry out hydrolysis copolycondensation on nano silver, quaternary ammonium silane (organic silicon bactericide) with surface activity, oil-soluble long-chain alkyl silane and nano silicon source substance (ethyl orthosilicate), and adds the prepared nano silver coated by the quaternary ammonium group/long-chain alkyl co-modified silica sol into a fluorine resin system, so that not only is no precipitate generated and the problem of settlement and delamination which is easy to occur when an inorganic metal component meets the organic phase can be solved, but also the nano silver coated by the quaternary ammonium group-modified silica sol (used as an inorganic-organic nano hybrid bactericidal component) is combined with a coating (film) and a coating prepared by epoxy fluorine-containing acrylate resin, and the coating (film) also has the effects of corrosion resistance, moisture resistance, sterilization and bacteriostasis.
Preparation of (I) quaternary ammonium silicasol coated nano silver (QAg-SiO2) bactericide
1.0g of nano Ag powder (Ningbo materials research institute, figure 2) with the average particle size of about 20-30nm, 10.02g of organosilicon bactericide (DC-5700) with the solid content of about 50 wt% and the active ingredient of (trimethoxysilylpropyl) octadecyl dimethyl ammonium chloride, 5.01g of dodecyl trimethoxy silane WD-10, 20.0g of ethyl orthosilicate and 50.0g of absolute ethyl alcohol solvent are weighed in sequence, stirred and mixed uniformly, then ultrasonic dispersion is carried out for 30min at room temperature by using an ultrasonic cleaner with the power of 1KW, the dispersion liquid is transferred to a three-necked bottle with a thermometer, a condenser tube and a stirrer, mechanically stirred, heated to 50 ℃, the pH of the system is adjusted to 3-4 by hydrochloric acid, and then 3.6g of deionized water is dripped while stirring for hydrolysis and polycondensation for 48 hours. After the reaction is finished, the pressure is reduced at 50 ℃ (P)Watch (A)0.8-0.9MPa), heating to 80 deg.C, removing low-boiling-point substance under reduced pressure, and heating the obtained product at 80 deg.C and PWatch (A)Vacuum drying at 0.7-0.9MPa for 1-2 hr to obtain light gray-light yellow nano powder, namely nano silver coated with quaternary ammonium silicasol, recorded as QAg-SiO2(see fig. 1, 3 and 4) for standby.
(II) antibacterial anticorrosion coating prepared based on silver-hetero quaternary ammonium-based nanosilicon sol and epoxy fluorine-containing acrylate resin EXAMPLE 1
(1) Based on QAg-SiO2Antibacterial anticorrosive paint prepared from epoxy fluorine-containing acrylate resin EFA-1
100.0g of a compound with a structure shown in formula (1) and R are weighed in sequencefIs perfluorooctylethyl, R ═ C18H37、M、M′＝CH3、M″＝H、A＝CH2OCH2CH(O)CH2Perfluorooctanes having a viscosity of 1100mPa.s, a solids content of about 60 wt.% and an epoxy group content (in terms of moles of epoxy groups per 100g of copolymer, the same applies hereinafter) of about 0.2%The ethyl methacrylate-co-stearyl methacrylate-co-allyl glycidyl ether terpolymer resin [ EFA-1, the fluorine monomer content (calculated by the mass fraction of the fluorine monomer in the copolymer) is about 40%]0.5g of dispersant BYK-ATU and 5.0g of nano silver QAg-SiO coated by quaternary ammonium silicasol225.0g of nano TiO2And 30.0g of butyl acetate, stirring and uniformly mixing, stirring and dispersing for 60min by using a high-speed dispersion machine with the rotating speed of 1000r/min, vacuumizing and defoaming to obtain 160.5g of mixture in total, which is recorded as paint A1; then 6.90g of polyetheramine D230, designated as curing agent B1, were weighed out in a ratio of 1:1 molar ratio of epoxy groups in EFA-1 contained in paint a1 to N — H bonds in paint B (organic amine).
(2) Preparation of antibacterial anticorrosive coating AC-1
And (3) priming treatment: h06-4 epoxy zinc-rich primer produced by Xian Tianyuan synthetic materials Co Ltd and CX105X curing agent are mixed according to the mass ratio of 18:5, the epoxy paint is evenly sprayed on the surface of the tinplate after sand blasting treatment by a spray gun after being evenly stirred and evenly mixed, the spraying amount is controlled so that the thickness of the dried coating is 25-30 mu m, and the mixture is cured for 4 hours at room temperature to obtain a primer coating sample D.
Finishing paint and a treatment process: uniformly stirring and mixing the paint A1 and the curing agent B1, and diluting the mixture by using a BA/MIBK (1:1, wt/wt) mixed solvent until the solid content is about 40 wt%, namely, the finishing paint working solution for spraying; then, taking a bottom coating sample D, and uniformly spraying the working solution on the surface of the sample D by using a spray gun with the pressure of 0.5MPa and the caliber of 0.8 mm; leveling at room temperature, drying for 30min, and baking at 120 deg.C for 30min to obtain antibacterial and anticorrosive coating, designated as AC-1, prepared from Ag-doped quaternary ammonium base nano silica sol and epoxy fluorine-containing acrylate resin EFA-1. The performance was measured by equilibration at room temperature (25 ± 2 ℃) and an ambient relative humidity RH of 48% for 24 h.
(3) The coating properties were evaluated by the following methods
Adhesion force: the measurement was carried out by an electric adhesion tester with reference to HG/T3792-2014 standard.
Impact resistance: reference is made to GB/T1732-1993, measured with an impact resistance device.
Flexibility: according to the method of GB/T1731-1993, the determination is carried out by a paint film elasticity tester.
Hardness: according to the method of GB/T6739-1996, pencil hardness is used for evaluation.
Sterilization and bacteriostasis: the antibacterial and bacteriostatic performance evaluation is carried out by taking staphylococcus aureus and escherichia coli as strains according to the HG/T3950-2007 method.
AC-1 Performance measurement results: the thickness of the coating (surface layer) is about 25.6 mu m, the adhesive force is grade 2, the impact resistance is more than or equal to 50cm, the flexibility is 2mm, the hardness is 2H, the antibacterial rate of the coating to staphylococcus aureus is about 95 percent, the antibacterial rate to escherichia coli is about 86.5 percent, and the contact angle WCA of water on the surface of the coating is 148.2 degrees.
Example 2
(1) Based on QAg-SiO2Antibacterial anticorrosive paint prepared from epoxy fluorine-containing acrylate resin EFA-2
100.0g of a compound of which the structure is shown as a formula (2) and R is weighed in sequencefIs perfluorohexylethyl, R ═ C4H9、M、M′＝CH3、M″＝H、A＝CH2OCH2CH(O)CH2Perfluorohexylethyl methacrylate-co-butyl methacrylate-co-styrene-co-allyl glycidyl ether quaternary copolymer resin (EFA-2, about 40% of fluorine monomer content) with viscosity of about 500mPa.s, solid content of about 50 wt% and epoxy group content of about 0.09%, 0.5g of dispersant BYK-ATU, 25.0g of quaternary ammonium silicon sol-coated nano silver QAg-SiO2And 10.0g of butyl acetate, stirring and uniformly mixing, stirring and dispersing for 30min by using a high-speed dispersion machine with the rotating speed of 1500r/min, and then vacuumizing and defoaming to obtain 135.5g of mixture in total, which is recorded as paint A2; then, 4.95g of polyetheramine D400, designated as curing agent B2, was weighed out in a ratio of 1:1.1 of the molar ratio of epoxy groups in EFA-2 contained in paint a2 to N — H bonds in paint B (organic amine).
(2) Preparation of antibacterial anticorrosive coating AC-2
And (3) priming treatment: as in example 1.
Finishing paint and a treatment process: uniformly stirring and mixing the paint A2 and the curing agent B2, and diluting the mixture by using a BA/MIBK (1:1, wt/wt) mixed solvent until the solid content is about 40 wt%, namely, the finishing paint working solution for spraying; then, taking a bottom coating sample D, and uniformly spraying the working solution on the surface of the sample D by using a spray gun with the pressure of 0.5MPa and the caliber of 0.8 mm; leveling at room temperature, drying for 30min, and baking at 130 deg.C for 30min to obtain antibacterial and anticorrosive coating, named AC-2, prepared from Ag-doped quaternary ammonium base nano silica sol and epoxy fluorine-containing acrylate resin EFA-2.
The performance was measured by equilibration at room temperature (25 ± 2 ℃) and an ambient relative humidity RH of 48% for 24 h. AC-2 Performance measurement results: the thickness of the coating (surface layer) is about 27.3 mu m, the adhesive force is grade 1, the impact resistance is more than or equal to 70cm, the flexibility is 1mm, the hardness is HB, the antibacterial rate of the coating to staphylococcus aureus is more than or equal to 99 percent, the antibacterial rate to escherichia coli is more than or equal to 99 percent, and the WCA is 110.1 degrees.
Example 3
(1) Based on QAg-SiO2Antibacterial anticorrosive paint prepared from epoxy fluorine-containing acrylate resin EFA-3
100.0g of a compound with a structure shown in formula (1) and R are weighed in sequencef1Is dodecafluoroheptyl, Rf2Is hexafluorobutyl, R ═ cyclohexyl, M, M ═ CH3、M″＝H、A＝COOCH2CH(O)CH2Dodecafluoroheptyl methacrylate-co-hexafluorobutyl methacrylate-co-cyclohexyl methacrylate-co-glycidyl acrylate quaternary copolymer resin (EFA-3, fluorine monomer content of about 60%) with viscosity of about 805mPa.s, solid content of about 55 wt% and epoxy group content of about 0.18%, 1.0g dispersant BYK-ATU, 18.0g quaternary ammonium silicasol coated nano silver QAg-SiO220.0g of hydrophobic Al2O3And 15.0g of BA/MIBK (1:1, wt/wt) mixed solvent, uniformly stirring, dispersing for 40min by using a high-speed dispersion machine with the rotating speed of 1000r/min, and then vacuumizing and defoaming to obtain 154.0g of mixture in total, which is marked as paint A3; then 3.81g of polyetheramine D230 and 3.72g of 4,4 are weighed out in a ratio of 1:1.1 of the molar ratio of epoxy groups in EFA-3 to N-H bonds in paint B (organic amine) contained in paint A3' -diaminodicyclohexylmethane, heated to melt, stirred and mixed uniformly, and the curing agent formed is denoted as curing agent B3.
(2) Preparation of antibacterial anticorrosive coating AC-3
And (3) priming treatment: as in example 1.
Finishing paint and a treatment process: uniformly stirring and mixing the paint A3 and the curing agent B3, and diluting the mixture by using a BA/MIBK (1:1, wt/wt) mixed solvent until the solid content is about 40 wt%, namely, the finishing paint working solution for spraying; then, taking a bottom coating sample D, and uniformly spraying the working solution on the surface of the sample D by using a spray gun with the pressure of 0.5MPa and the caliber of 0.8 mm; leveling at room temperature, drying for 30min, and baking at 150 deg.C for 20min to obtain antibacterial and anticorrosive coating, designated as AC-3, prepared from Ag-doped quaternary ammonium base nanosilicon sol and epoxy fluorine-containing acrylate resin EFA-3.
The performance was measured by equilibration at room temperature (25. + -. 2 ℃ C.) and a relative humidity RH of 48% for 24 h. AC-3 Performance measurement results: the thickness of the coating (surface layer) is about 26.3 mu m, the adhesive force is grade 1, the impact resistance is more than or equal to 70cm, the flexibility is 1mm, the hardness is 2H, the antibacterial rate of the coating to staphylococcus aureus is more than or equal to 99 percent, the antibacterial rate to escherichia coli is more than or equal to 99 percent, and the WCA is 139.5 degrees.
Example 4
(1) Based on QAg-SiO2Antibacterial anticorrosive paint prepared from epoxy fluorine-containing acrylate resin EFA-4
100.0g of a compound with a structure shown in formula (1) and R are weighed in sequencef1Is perfluorohexylethyl, Rf2Is a perfluoropolyether group, R ═ C12H25、M、M′＝CH3、M″＝H、a＝0、b＝3、A＝-CH2O(C3H6O)3CH2CH(O)CH2Perfluorohexylethyl methacrylate-co-perfluoropolyether acrylate (Mn ═ 1000) -co-decamethylene methacrylate-co-allylpolyoxypropylene epoxy ether penta-copolymer resin having a viscosity of about 900mpa.s, a solid content of 60 wt% and an epoxy content of about 0.2% (EFA-4,about 40 percent of total amount of F monomer), 0.6g of dispersant BYK-161, 12.0g of nano silver QAg-SiO coated by quaternary ammonium silicasol225.0g hydrophobic nano Al (OH)3And 20.0g of BA/PMA (3:1, wt/wt) mixed solvent, uniformly stirring, dispersing for 45min by using a high-speed dispersion machine with the rotating speed of 1000r/min, and then vacuumizing and defoaming to obtain 157.60g of mixture in total, which is recorded as paint A4; then 5.11g of isophorone diamine was weighed out as curing agent B4, in a ratio of 1:1 of the molar ratio of epoxy groups in EFA-4 contained in paint A4 to N-H bonds in paint B (organic amine).
(2) Preparation of antibacterial anticorrosive coating AC-4
And (3) priming treatment: as in example 1.
Finishing paint and a treatment process: uniformly stirring and mixing the paint A4 and the curing agent B4, and diluting the mixture by using a BA/MIBK (1:1, wt/wt) mixed solvent until the solid content is about 40 wt%, namely, the finishing paint working solution for spraying; then, taking a bottom coating sample D, and uniformly spraying the working solution on the surface of the sample D by using a spray gun with the pressure of 0.5MPa and the caliber of 0.8 mm; leveling at room temperature, drying for 30min, and baking at 130 deg.C for 30min to obtain antibacterial and anticorrosive coating, designated as AC-4, prepared from Ag-doped quaternary ammonium base nano silica sol and epoxy fluorine-containing acrylate resin EFA-4.
The performance was measured by equilibration at room temperature (25. + -. 2 ℃ C.) and a relative humidity RH of 48% for 24 h. AC-4 Performance measurement results: the thickness of the coating (surface layer) is about 27.5 mu m, the adhesive force is grade 1, the impact resistance is more than or equal to 60cm, the flexibility is 1mm, the hardness is 2H, the antibacterial rate of the coating to staphylococcus aureus is more than or equal to 99 percent, the antibacterial rate to escherichia coli is about 99 percent, and the WCA is 143.9 degrees.
Example 5
Replacing EFA-3 in example 3 with equal amount of heptadecafluorodecyl methacrylate-co-hexafluorobutyl methacrylate-co-allyl glycidyl ether terpolymer resin (EFA-5) with viscosity of about 960mPa.s, solid content of 60 wt%, epoxy content of about 0.2% and fluorine monomer content of about 86% to obtain paint A5; the rest were tested as in example 3.
The performance of the antibacterial and anticorrosive coating AC-5 prepared on the basis of EFA-5 and the curing agent B3 is as follows: the thickness of the coating (surface layer) is about 25.6 mu m, the adhesive force is grade 2, the impact resistance is more than or equal to 50cm, the flexibility is 1mm, the hardness is 2H, the antibacterial rate of the coating to staphylococcus aureus is more than or equal to 99 percent, the antibacterial rate to escherichia coli is more than or equal to 99 percent, and the WCA is 141.2 degrees.
Example 6 (comparative example 1 of example 2)
Nano-silver QAg-SiO coated with quaternary ammonium silicasol from example 22Paint A was prepared by replacing the same amount of silver powder with the same amount of silver powder, and using the same raw materials and preparation method as in example 2. As a result: the paint A is settled and layered after being placed for 24h, the lower layer is the grey brown silver powder precipitate, and the upper layer is the organic fluororesin. The paints A1, A2, A3, A4 and A5 prepared by the invention examples 1,2,3, 4 and 5 are not layered and precipitated after being placed for a plurality of days.
In addition, the paint A and the curing agent B2 in the example 6 are stirred and mixed uniformly and diluted by the BA/MIBK mixed solvent, so that the nano silver powder is more quickly settled due to the reduction of the viscosity of the system, most of the silver powder is deposited at the bottom of the storage tank of the spray gun and cannot be sprayed or uniformly distributed in the paint coating (AC-6), and the sterilizing effect of the coating is poor. AC-6 Performance measurement results: the thickness of the coating (surface layer) is about 27.8 mu m, the adhesive force is grade 1, the impact resistance is more than or equal to 70cm, the flexibility is 1mm, the hardness is HB, the antibacterial rate of the coating on staphylococcus aureus is about 90 percent, the antibacterial rate on escherichia coli is about 80 percent, and the WCA is 116.5 degrees.
Example 7 (comparative example 2 of example 2)
Nano-silver QAg-SiO coated without quaternary ammonium silica sol as in example 22Other raw materials and preparation methods are the same as example 2, paint A is prepared, curing is carried out by using curing agent B2 (the priming treatment, the finish paint, the treatment process and the like are the same as example 2), the prepared coating is balanced for 24 hours at room temperature (25 +/-2 ℃) and RH (48%), and performance measurement is carried out: the thickness of the coating (surface layer) is about 26.4 mu m, the adhesive force is grade 1, the impact resistance is more than or equal to 70cm, the flexibility is 1mm, the hardness is B, the antibacterial rate of the coating to staphylococcus aureus and escherichia coli is not obvious, and the WCA is 113.6 degrees.
By pairsAs can be seen, the nano silver (QAg-SiO) coated by the quaternary ammonium silicasol2) The epoxy fluorine-containing acrylate resin coating system is added, so that the effect of preventing the inorganic nano silver powder from precipitating is achieved; in addition, the invention is based on nano silver (QAg-SiO) coated by quaternary ammonium silicasol2) The antibacterial and anticorrosive paint prepared from the epoxy fluorine-containing acrylate resin can endow the coating with waterproof and antifouling performances, effectively integrates the advantages and performances of the inorganic-organic hybrid bactericide through uniform dispersion of nano-silver, and improves the antibacterial and bacteriostatic performances of the coating.
Claims (10)
1. The silver-mixed fluororesin antibacterial anticorrosive paint is characterized in that: the antibacterial anticorrosive paint comprises epoxy fluorine-containing acrylate resin and silver hybrid quaternary ammonium base nano silica sol dispersed in the epoxy fluorine-containing acrylate resin; the silver hybrid quaternary ammonium base nano silica sol is nano silver coated by quaternary ammonium silica sol.
2. The silver-heterofluoride antibacterial anticorrosive paint according to claim 1, characterized in that: the antibacterial anticorrosive paint consists of a paint A and a paint B; the paint A consists of 100 parts by mass of epoxy fluorine-containing acrylate resin, 5-25 parts by mass of quaternary ammonium silicasol coated nano silver, 0-25 parts by mass of hydrophobic nano pigment filler, 0.1-1.0 part by mass of wetting dispersant and solvent; the paint B is an organic amine curing agent, and the quantity ratio of epoxy groups in the epoxy fluorine-containing acrylate resin contained in the paint A to N-H bonds in the paint B is 1: 1-1.1.
3. The silver-heterofluorine-resin antibacterial anticorrosive paint according to claim 1 or 2, characterized in that: the epoxy fluorine-containing acrylate resin comprises one or more of multipolymers with the structures shown as formula (1) and formula (2):
wherein n, m, x and y are integers more than or equal to 0; rfIs selected from C4-C14Containing fluorine ofOne or more of alkyl; r is C1-C18One of the alkyl groups of (a); m, M 'and M' are H or CH3；
a. b is any integer of 0-10, and 10 is more than or equal to a + b > 0.
4. The silver-heterofluorine-resin antibacterial anticorrosive paint according to claim 1 or 2, characterized in that: the multipolymer contained in the epoxy fluorine-containing acrylate resin is selected from C4-14Fluoroalkyl (meth) acrylate-co-alkenyl epoxy compound copolymer, C4-14Fluoroalkyl (meth) acrylates-co-C1-18Alkyl (meth) acrylate-co-alkenyl epoxy compound copolymer, C4-14Fluoroalkyl (meth) acrylate-co-styrene-co-alkenyl epoxy compound copolymer, C4-14Fluoroalkyl (meth) acrylates-co-C1-18One or more of alkyl (meth) acrylate-styrene-co-alkenyl epoxy compound copolymers; the solid content of the epoxy fluorine-containing acrylate resin is 50-60%, the viscosity is 500-1500mPa.s, the epoxy group content is 0.09-0.2%, and the fluorine monomer content is 40-86%.
5. The silver-heterofluoride antibacterial anticorrosive paint according to claim 4, characterized in that: said C is4-14The fluoroalkyl (meth) acrylate is selected from one or more of perfluorooctylethyl (meth) acrylate, perfluorohexylethyl (meth) acrylate, dodecafluoroheptyl (meth) acrylate, hexafluorobutyl (meth) acrylate, perfluoropolyether (meth) acrylate having an average molecular weight Mn of 1000-3000; c1-18The alkyl (meth) acrylate is selected from methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, propyl (meth) acrylateOne or two of isobornyl enoate; the alkenyl epoxy compound is one selected from allyl glycidyl ether, glycidyl (meth) acrylate, allyl polyoxyethylene epoxy ether, and allyl polyoxypropylene epoxy ether.
6. The silver-heterofluoride antibacterial anticorrosive paint according to claim 2, characterized in that: the organic amine curing agent is at least one of organic amines containing 2-3 amino groups in molecules.
7. The silver-heterofluorine-resin antibacterial anticorrosive paint according to claim 1 or 2, characterized in that: the nano silver coated by the quaternary ammonium silicasol is prepared by carrying out hydrolytic polycondensation reaction on nano silver, quaternary ammonium silane, long-chain alkyl silane and tetraethoxysilane.
8. The silver-heterofluoride antibacterial anticorrosive paint according to claim 7, characterized in that: in the hydrolytic polycondensation reaction, the use amounts of nano silver, quaternary ammonium silane, long-chain alkyl silane and ethyl orthosilicate are respectively 1 part, 5-10 parts, 0-10 parts and 10-20 parts by mass; the active ingredient of the quaternary ammonium silane is (trimethoxysilylpropyl) octadecyl dimethyl ammonium chloride or [3- (trimethoxysilylpropyl) -2-hydroxy-oxypropyl ] octadecyl dimethyl quaternary ammonium salt.
9. A method for preparing the silver heterofluoro resin antibacterial anticorrosive paint according to claim 1 or 2, which is characterized in that: the method comprises the following steps:
1) mixing the weighed epoxy fluorine-containing acrylate resin, the nano silver coated by the quaternary ammonium silica sol, the hydrophobic nano pigment filler, the wetting dispersant and the solvent, stirring for dispersion, and then vacuumizing for defoaming to obtain a mixture, namely a paint A;
2) weighing the organic amine curing agent according to the mass ratio of epoxy groups in the epoxy fluorine-containing acrylate resin in the paint A to N-H bonds in the organic amine curing agent of 1:1-1.1, thus obtaining paint B;
3) mixing paint A and paint B.
10. The silver-doped fluororesin antibacterial anticorrosive coating is characterized in that: the antibacterial and anticorrosive coating is prepared by diluting, coating and curing the silver heterofluorine resin antibacterial and anticorrosive coating according to claim 1 or 2.
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