CN117264501B - Antibacterial powder coating and preparation method thereof - Google Patents
Antibacterial powder coating and preparation method thereof Download PDFInfo
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- CN117264501B CN117264501B CN202311548746.1A CN202311548746A CN117264501B CN 117264501 B CN117264501 B CN 117264501B CN 202311548746 A CN202311548746 A CN 202311548746A CN 117264501 B CN117264501 B CN 117264501B
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- 238000000576 coating method Methods 0.000 title claims abstract description 95
- 239000011248 coating agent Substances 0.000 title claims abstract description 92
- 239000000843 powder Substances 0.000 title claims abstract description 88
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical class [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 111
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 57
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 57
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract description 25
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 18
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 22
- -1 polybutylene adipate Polymers 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 230000000845 anti-microbial effect Effects 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 10
- VRLDVERQJMEPIF-UHFFFAOYSA-N dbdmh Chemical compound CC1(C)N(Br)C(=O)N(Br)C1=O VRLDVERQJMEPIF-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000004599 antimicrobial Substances 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 239000003973 paint Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000012858 packaging process Methods 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000010703 silicon Chemical group 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 238000002802 antimicrobial activity assay Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
Abstract
The invention discloses an antibacterial powder coating and a preparation method thereof, and relates to the field of powder coatings, wherein the antibacterial powder coating is prepared from the following raw materials in parts by weight: 30-60 parts of acrylic resin, 20-30 parts of modified barium sulfate and 30-60 parts of epoxy resin; 2-8 parts of curing agent; 1-5 parts of dispersing agent; the modified barium sulfate is prepared from the following raw materials: barium sulfate, diethylene glycol dimethyl ether, DOPO, vinyltrimethoxysilane, azobisisobutyronitrile. The application has the effect of improving the antibacterial property of the powder coating.
Description
Technical Field
The invention relates to the field of powder coatings, in particular to an antibacterial powder coating and a preparation method thereof.
Background
The powder coating is a solid powder synthetic resin coating composed of a resin, a curing agent, an inorganic filler, a pigment, an auxiliary agent, etc., and unlike a general solvent-based coating and a water-based coating, the dispersion medium of the powder coating is not an organic solvent or water, but air. The powder coating can form a film by 100%, has no solvent pollution and water pollution, is a real environment-friendly coating, has the characteristics of low energy consumption and recoverability, and is widely applied to the fields of building materials, household appliances, engineering machinery, electronics, electric and industrial corrosion prevention and the like.
The existing powder coating is easy to be damaged on the surface of a coating film under the conditions that the weather is moist and the temperature is suitable for growth of bacteria or other harmful microorganisms, such as mold, and the like, so that the coating film is discolored, pulverized and shed, the most basic protection and decoration functions on a substrate are lost, and the most important is that the harmful bacteria can influence the health of people if growing and propagating on the coating film.
Disclosure of Invention
In order to improve the antibacterial performance of the powder coating, the application provides an antibacterial powder coating and a preparation method thereof.
In a first aspect, the present application provides an antimicrobial powder coating that employs the following technical scheme:
an antibacterial powder coating is prepared from the following raw materials in parts by weight: 30-60 parts of acrylic resin, 20-30 parts of modified barium sulfate and 30-60 parts of epoxy resin; 2-8 parts of curing agent; 1-5 parts of dispersing agent; the modified barium sulfate is prepared from the following raw materials: barium sulfate, diethylene glycol dimethyl ether, DOPO, vinyltrimethoxysilane, azobisisobutyronitrile.
Through adopting above-mentioned technical scheme, barium sulfate has certain antibacterial property, this application is through adding the packing of the barium sulfate after the modification as powder coating, pack between acrylic resin and epoxy, improve the thickness of coating, make the two inseparable bonding, make powder coating form the three-dimensional network structure that interpenetrating density is formed after the film, thereby improve the crosslinked density and the hardness of film, and the barium sulfate after the modification has higher intensity and further improves the antibacterial effect of barium sulfate, the area of contact of modified barium sulfate increase and acrylic resin and epoxy forms more physical bonding points, and then improve the antibacterial effect after the powder coating formed the film.
Preferably, the preparation method of the modified barium sulfate comprises the following steps: mixing and stirring 40-80 parts by weight of diethylene glycol dimethyl ether and 40-60 parts by weight of DOPO, heating, adding 20-30 parts by weight of vinyltrimethoxysilane and 0.1-0.5 part by weight of azodiisobutyronitrile, mixing and stirring, washing, filtering, adding 30-50 parts by weight of barium sulfate and 80-120 parts by weight of methanol, heating for reaction, filtering to remove solvent, drying, and grinding into powder to obtain the modified barium sulfate.
Through adopting above-mentioned technical scheme, this application forms silicon phosphorus coupling modifier through diethylene glycol dimethyl ether, DOPO, vinyl trimethoxy silane, azodiisobutyronitrile and carries out the modification to the barium sulfate surface, contain P-H bond in the DOPO, with the olefin reaction in the vinyl trimethoxy silane, vinyl trimethoxy silane contains the silane simultaneously, make barium sulfate surface smooth, hole quantity is more and the aperture is great, DOPO, vinyl trimethoxy silane carries out the grafting modification to barium sulfate, make modified barium sulfate and diethylene glycol dimethyl ether, DOPO and vinyl trimethoxy silane's compatibility is good, barium sulfate can more evenly disperse in the powder coating, thereby improve the antibacterial effect of the paint film that the powder coating formed.
Preferably, the weight ratio of DOPO, vinyl trimethoxy silane and barium sulfate is 1: (0.42-0.48): (0.84-0.96).
By adopting the technical scheme, when DOPO, vinyl trimethoxy silane and barium sulfate are in a specific weight ratio, DOPO and vinyl trimethoxy silane form a steric effect, so that the aggregation and migration of the barium sulfate can be well prevented, the modified barium sulfate can be uniformly dispersed in the components, and a paint film formed by the powder coating further has a good antibacterial effect; the hardness of the paint film can also be improved.
Preferably, the acrylic resin is modified acrylic resin, and the preparation method of the modified acrylic resin comprises the following steps: heating and melting 15-45 parts by weight of polybutylene adipate glycol, 8-16 parts by weight of trimethylolpropane and 10-20 parts by weight of 1, 4-butanediol, cooling and stirring, adding 20-60 parts by weight of acrylic resin, 40-60 parts by weight of 2, 2-dimethylolpropionic acid and 15-25 parts by weight of N, N-dimethylformamide, continuously heating and stirring, sequentially adding 20-30 parts by weight of dibromodimethylhydantoin, 30-50 parts by weight of triethylamine and 0.5-1.5 parts by weight of antioxidant, mixing and stirring, washing and drying to obtain the modified acrylic resin.
Through adopting above-mentioned technical scheme, this application is through carrying out the modification to acrylic resin, introduces active groups such as hydroxyl, silicon hydroxyl in acrylic resin, adopts the mode of physical blending, improves acrylic resin and epoxy's bonding strength through valence bond combination, has strengthened modified acrylic resin's stability, makes the antibacterial performance of film that powder coating rope formed further improve, has excellent hydrophobic water resistance simultaneously.
Preferably, the weight ratio of the polybutylene adipate glycol, the acrylic resin, the 2, 2-dimethylolpropionic acid and the dibromodimethylhydantoin is (0.9-1.05): 1: (1.05-1.2): (0.6-0.7).
By adopting the technical scheme, when the polybutylene adipate glycol, the acrylic resin, the 2, 2-dimethylolpropionic acid and the dibromo-dimethylhydantoin are grafted into the acrylic resin better as an antibacterial agent in a specific weight ratio, the antibacterial effect is better achieved, and simultaneously the polybutylene adipate glycol, the 2, 2-dimethylolpropionic acid and the dibromo-dimethylhydantoin can be uniformly distributed in the acrylic resin after being blended, and the four components are synergistic to improve the water resistance of the powder coating.
Preferably, the weight ratio of the modified acrylic ester, the modified barium sulfate and the epoxy resin is (1.2-1.4): (0.55-0.65): 1.
by adopting the technical scheme, when the modified acrylic ester, the modified barium sulfate and the epoxy resin are in a specific weight ratio, the structural stability of the powder coating in the transportation process, the packaging process or the long-term storage process is further improved, and the antibacterial effect and the water resistance of a paint film formed by the powder coating are improved.
Preferably, the molecular weight of the acrylic resin is 7000.
Preferably, the curing agent is beta-hydroxyalkylamide.
Preferably, the dispersant is microcrystalline paraffin.
By adopting the technical scheme, the antibacterial performance of the powder coating can be further improved by selecting proper acrylic resin dispersing agent and curing agent.
In a second aspect, the preparation method of the antibacterial powder coating provided by the application adopts the following technical scheme:
the preparation method of the antibacterial powder coating comprises the following steps: heating and uniformly mixing epoxy resin, modified barium sulfate and acrylic resin, extruding and granulating; adding a curing agent and a dispersing agent, extruding, granulating, tabletting, crushing and screening to obtain the powder coating.
By adopting the technical scheme, the preparation method of the powder coating has the characteristics of simple steps and convenient operation, and is beneficial to the preparation of the antibacterial property of a paint film formed by the powder coating.
In summary, the present application has the following beneficial technical effects:
1. according to the modified barium sulfate powder coating, the modified barium sulfate is added to serve as a filler of the powder coating, the modified barium sulfate is filled between the acrylic resin and the epoxy resin, the thickness of the coating film is increased, the acrylic resin and the epoxy resin are tightly adhered, the powder coating forms a three-dimensional network structure which is compact in an interpenetrating manner after a film is formed by the powder coating, so that the crosslinking density and hardness of the film are improved, the modified barium sulfate has higher strength, the antibacterial effect of the barium sulfate is further improved, the contact area between the modified barium sulfate and the acrylic resin and the epoxy resin is increased, more physical adhesion points are formed, and the antibacterial effect of the powder coating after the film is formed is further improved.
2. According to the preparation method, the silicon-phosphorus coupling modifier is formed by diethylene glycol dimethyl ether, DOPO, vinyl trimethoxy silane and azo diisobutyronitrile to modify the surface of barium sulfate, the DOPO contains P-H bond and reacts with olefin in the vinyl trimethoxy silane, meanwhile, the vinyl trimethoxy silane contains silane, so that the surface of modified barium sulfate is smooth, the number of holes is large, the aperture is large, the DOPO and the vinyl trimethoxy silane carry out grafting modification on the barium sulfate, the compatibility of the modified barium sulfate with diethylene glycol dimethyl ether, DOPO and the vinyl trimethoxy silane is good, and the barium sulfate can be uniformly dispersed into the powder coating, so that the antibacterial effect of a paint film formed by the powder coating is improved.
Detailed Description
The present application is described in further detail below in connection with examples and comparative examples.
Examples
Example 1
The preparation method of the antibacterial powder coating comprises the following steps:
adding 30g of epoxy resin, 20g of modified barium sulfate and 30g of acrylic resin into a reaction kettle, heating to 120 ℃, stirring for 10min at the rotating speed of 800r/min, transferring into a screw extruder, extruding and granulating; granulating, adding the granulated powder, 2g of beta-hydroxyalkylamide curing agent and 1g of microcrystalline paraffin dispersing agent into a stirrer together, stirring for 30min at the temperature of 120 ℃ and the rotating speed of 1000r/min, tabletting in a tablet press, crushing and screening after stirring, and obtaining the powder coating. The epoxy resin is XU-Chen E-44, XC-214741, and has a solid content of 80%; the acrylic resin is Han Hua S-70, the molecular weight is 7000, the viscosity is 700Pa.s, and the acid value is 218mgKOH/g.
The preparation method of the modified barium sulfate comprises the following steps:
adding 40g of diethylene glycol dimethyl ether and 40g of DOPO into a stirrer, mixing and stirring for 5min, heating to 80 ℃, adding 20g of vinyltrimethoxysilane and 0.1g of azobisisobutyronitrile, mixing and stirring for 10min, washing with cyclohexane, filtering to remove the solvent, adding 30g of barium sulfate and 80g of methanol, heating to 60 ℃, stirring for 24h, filtering, removing the solvent, adding into a baking oven, drying for 2h at the temperature of 100 ℃, and grinding into powder to obtain the modified barium sulfate.
Example 2
The preparation method of the antibacterial powder coating comprises the following steps:
60g of epoxy resin, 30g of modified barium sulfate and 60g of acrylic resin are put into a reaction kettle, the temperature is raised to 120 ℃, the mixture is stirred for 10min under the condition of the rotating speed of 800r/min, and then the mixture is transferred into a screw extruder for extrusion granulation; granulating, adding the granulated powder, 8g of beta-hydroxyalkylamide curing agent and 5g of microcrystalline paraffin dispersing agent into a stirrer together, stirring for 30min at the temperature of 120 ℃ and the rotating speed of 1000r/min, tabletting in a tablet press, crushing and screening after stirring, and obtaining the powder coating. The epoxy resin is XU-Chen E-44, XC-214741, and has a solid content of 80%; the acrylic resin is Han Hua S-70, the molecular weight is 7000, the viscosity is 700Pa.s, and the acid value is 218mgKOH/g.
The preparation method of the modified barium sulfate comprises the following steps:
adding 40g of diethylene glycol dimethyl ether and 40g of DOPO into a stirrer, mixing and stirring for 5min, heating to 80 ℃, adding 20g of vinyltrimethoxysilane and 0.1g of azobisisobutyronitrile, mixing and stirring for 10min, washing with cyclohexane, filtering to remove the solvent, adding 30g of barium sulfate and 80g of methanol, heating to 60 ℃, stirring for 24h, filtering, removing the solvent, adding into a baking oven, drying for 2h at the temperature of 100 ℃, and grinding into powder to obtain the modified barium sulfate.
Example 3
The preparation method of the antibacterial powder coating comprises the following steps:
adding epoxy resin, modified barium sulfate and acrylic resin into a reaction kettle, heating to 120 ℃, stirring for 10min at the rotating speed of 800r/min, transferring into a screw extruder, extruding and granulating; granulating, adding into a stirrer together with a curing agent and a dispersing agent, stirring for 30min at 120 ℃ and a rotating speed of 1000r/min, tabletting in a tablet press after stirring, crushing and screening to obtain the powder coating. The epoxy resin is XU-Chen E-44, XC-214741, and has a solid content of 80%; the acrylic resin is Han Hua S-70, the molecular weight is 7000, the viscosity is 700Pa.s, and the acid value is 218mgKOH/g.
The preparation method of the modified barium sulfate comprises the following steps:
adding 40g of diethylene glycol dimethyl ether and 40g of DOPO into a stirrer, mixing and stirring for 5min, heating to 80 ℃, adding 20g of vinyltrimethoxysilane and 0.1g of azobisisobutyronitrile, mixing and stirring for 10min, washing with cyclohexane, filtering to remove the solvent, adding 30g of barium sulfate and 80g of methanol, heating to 60 ℃, stirring for 24h, filtering, removing the solvent, adding into a baking oven, drying for 2h at the temperature of 100 ℃, and grinding into powder to obtain the modified barium sulfate.
Example 4
A method for preparing an antibacterial powder coating, which is different from example 3 in that in the method for preparing modified barium sulfate:
putting 80g of diethylene glycol dimethyl ether and 60g of DOPO into a stirrer, mixing and stirring for 5min, heating to 80 ℃, adding 30g of vinyltrimethoxysilane and 0.5g of azobisisobutyronitrile, mixing and stirring for 10min, washing with cyclohexane, filtering to remove the solvent, adding 50g of barium sulfate and 120g of methanol, heating to 60 ℃, stirring for 24h, filtering, removing the solvent, putting into a baking oven, drying for 2h at 100 ℃, and grinding into powder to obtain the modified barium sulfate.
Example 5
A preparation method of an antibacterial powder coating material was different from example 3 in that in the method of preparing modified barium sulfate, the input amount of DOPO was 50g, the input amount of vinyltrimethoxysilane was 21g, and the input amount of barium sulfate was 42g.
Example 6
A preparation method of an antibacterial powder coating material was different from example 3 in that in the method of preparing modified barium sulfate, the input amount of DOPO was 50g, the input amount of vinyltrimethoxysilane was 24g, and the input amount of barium sulfate was 48g.
Example 7
A method for preparing an antibacterial powder coating, which is different from example 6 in that the acrylic resin is replaced by a modified acrylic resin in equal amount, and the method for preparing the modified acrylic resin is as follows:
15g of polybutylene adipate glycol, 8g of trimethylolpropane and 10g of 1, 4-butanediol are put into a heating pot to be heated to 110 ℃, then cooled to 50 ℃, stirred for 10min at the rotation speed of 280r/min, then 20g of acrylic resin, 40g of 2, 2-dimethylolpropionic acid and 15g of N, N-dimethylformamide are added to be continuously heated to 70 ℃ to be stirred for 60min, then 20g of dibromodimethylhydantoin, 30g of triethylamine and 0.5g of antioxidant 1010 are sequentially added to be mixed and stirred for 30min, after the solution is removed after washing, the mixture is put into an oven, and the mixture is dried for 2h at the temperature of 80 ℃ to obtain the modified acrylic resin. The polybutylene adipate glycol is selected from Shanghai Hongshui chemical engineering Co., ltd, and the model is 25103-87-1.
Example 8
A method for preparing an antibacterial powder coating, which is different from example 6 in that the acrylic resin is replaced by a modified acrylic resin in equal amount, and the method for preparing the modified acrylic resin is as follows:
45g of polybutylene adipate glycol, 16g of trimethylolpropane and 20g of 1, 4-butanediol are put into a heating pot to be heated to 110 ℃, then cooled to 50 ℃, stirred for 10min at the rotation speed of 280r/min, then 60g of acrylic resin, 60g of 2, 2-dimethylolpropionic acid and 25g of N, N-dimethylformamide are added to be continuously heated to 70 ℃ to be stirred for 60min, then 30g of dibromodimethylhydantoin, 50g of triethylamine and 1.5g of antioxidant 1010 are sequentially added to be mixed and stirred for 30min, the solution is removed after washing, and then the mixture is put into an oven to be dried for 2h at the temperature of 80 ℃ to obtain the modified acrylic resin. The polybutylene adipate glycol is selected from Shanghai Hongshui chemical engineering Co., ltd, and the model is 25103-87-1.
Example 9
A preparation method of an antibacterial powder coating material was different from example 8 in that in the preparation of the modified acrylic ester, the charged amount of polybutylene adipate glycol was 36g, the charged amount of acrylic resin was 40g, the charged amount of 2, 2-dimethylolpropionic acid was 42g, and the charged amount of dibromodimethylhydantoin was 24g.
Example 10
A preparation method of an antibacterial powder coating material was different from example 8 in that in the preparation of the modified acrylic ester, the charged amount of polybutylene adipate glycol was 42g, the charged amount of acrylic resin was 40g, the charged amount of 2, 2-dimethylolpropionic acid was 48g, and the charged amount of dibromodimethylhydantoin was 28g.
Example 11
A preparation method of an antibacterial powder coating is different from example 10 in that in the preparation process of the powder coating, the input amount of modified acrylic ester is 48g, the input amount of modified barium sulfate is 22g, and the input amount of epoxy resin is 40g.
Example 12
A preparation method of an antibacterial powder coating is different from example 10 in that in the preparation process of the powder coating, the input amount of modified acrylic ester is 56g, the input amount of modified barium sulfate is 26g, and the input amount of epoxy resin is 40g.
Comparative example
Comparative example 1
A method for preparing an antibacterial powder coating, which is different from example 3 in that the modified barium sulfate is replaced by the same amount of barium sulfate.
Comparative example 2
A method for preparing an antibacterial powder coating, which is different from example 3 in that the modified barium sulfate is replaced with titanium dioxide in equal amount.
Comparative example 3
A method for preparing the antibacterial powder coating is different from example 3 in that the acrylic resin is replaced by a polyester resin with the same amount, and the polyester resin is specifically 9005-6-73 of the brand produced by kepler in Shandong province.
Comparative example 4
A method for preparing the antibacterial powder coating is different from example 3 in that the epoxy resin is replaced by the polyester resin with the same amount, and the polyester resin is specifically 9005-6-73 of the brand produced by kepler in Shandong province.
Comparative example 5
A method for preparing an antibacterial powder coating, which is different from example 3 in that the acrylic resin is replaced with an epoxy resin in equal amount.
Comparative example 6
A method for preparing an antimicrobial powder coating, which differs from example 3 in that the epoxy resin is replaced by an acrylic resin in equal amounts.
Performance test:
and (3) respectively spraying the powder coatings obtained in the examples 1-12 and the comparative examples 1-6 on ferrite magnetic rings preheated in an oven at 200 ℃ in advance by a high-voltage electrostatic spraying mode under the same spraying pressure, wherein the thickness of the coating is 200 mu m, the curing temperature is 200 ℃, and the curing time is 5min, so as to obtain a sample to be tested.
Hardness testing: the samples to be tested prepared in examples 1 to 12 and comparative examples 1 to 6 were tested with reference to GB/T6739-2006 paint film hardness measured by the paint and varnish pencil method;
antibacterial properties: the test samples prepared in examples 1-12 and comparative examples 1-6 were tested for staphylococcus aureus antimicrobial according to the national standard GB/T21866-2008 antimicrobial coating (paint film) antimicrobial assay and antimicrobial effect;
water resistance: the samples to be tested obtained in examples 1 to 12 and comparative examples 1 to 6 were tested with reference to GB/T1733-1993 paint film Water resistance assay. Distilled water is added into the glass water tank, and the water is kept in a boiling state until the test is finished. The paint template is placed in a glass water tank, and 2/3 of the length of the paint template is ensured to be soaked in water. Any phenomena such as light loss, color change, foaming, wrinkling, falling off, rust and the like in the paint template are the longest boiling water resistant time.
| Hardness of | Antibacterial property% | The longest water resistance is the wastewater resistance time min | |
| Example 1 | 4H | 93.6 | 144 |
| Example 2 | 4H | 93.4 | 142 |
| Example 3 | 4H | 93.7 | 146 |
| Example 4 | 4H | 93.9 | 145 |
| Example 5 | 4H | 95.1 | 161 |
| Example 6 | 4H | 95.3 | 160 |
| Example 7 | 5H | 98.8 | 168 |
| Example 8 | 5H | 98.6 | 166 |
| Example 9 | 5H | 99.4 | 175 |
| Example 10 | 5H | 99.1 | 173 |
| Example 11 | 5H | 99.6 | 184 |
| Example 12 | 5H | 99.8 | 186 |
| Comparative example 1 | 3H | 88.9 | 121 |
| Comparative example 2 | 3H | 90.1 | 116 |
| Comparative example 3 | 2H | 89.4 | 114 |
| Comparative example 4 | 2H | 88.4 | 105 |
| Comparative example 5 | 3H | 86.8 | 112 |
| Comparative example 6 | 3H | 88.4 | 108 |
According to the data comparison of the examples 1-3 and the comparative examples 1-6, the modified barium sulfate is added as the filler of the powder coating, the modified barium sulfate is filled between the acrylic resin and the epoxy resin, the thickness of the coating film is increased, the modified barium sulfate and the epoxy resin are tightly adhered, the powder coating forms a three-dimensional interpenetrating network structure after forming the coating film, the crosslinking density and the hardness of the coating film are improved, the modified barium sulfate has higher strength and further improves the antibacterial effect of the barium sulfate, the contact area of the modified barium sulfate with the acrylic resin and the epoxy resin is increased, more physical adhesion points are formed, and the antibacterial effect of the powder coating after forming the coating film is further improved.
According to the data comparison of the examples 3-6, when DOPO, vinyl trimethoxy silane and barium sulfate are mixed in a specific weight ratio, the DOPO and the vinyl trimethoxy silane form a steric hindrance effect, so that the aggregation and migration of the barium sulfate can be well prevented, the modified barium sulfate can be uniformly dispersed in the components, and a paint film formed by the powder coating further has a good antibacterial effect; the hardness of the paint film can also be improved.
According to the data comparison of examples 7-10, the acrylic resin is modified, active groups such as hydroxyl, silicon hydroxyl and the like are introduced into the acrylic resin, and the bonding strength of the acrylic resin and the epoxy resin is improved through valence bond combination in a physical blending mode, so that the stability of the modified acrylic resin is enhanced, the antibacterial performance of a paint film formed by the powder coating is further improved, and meanwhile, the paint film has excellent hydrophobic water resistance.
According to the data comparison of examples 11-12, when the modified acrylic ester, the modified barium sulfate and the epoxy resin are mixed according to a specific weight ratio, the structural stability of the powder coating in the transportation process, the packaging process or the long-term storage process is further improved, and the antibacterial effect and the water resistance of a paint film formed by the powder coating are improved.
The present embodiment is merely illustrative of the present application and is not limiting of the present application, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as necessary, but are protected by patent laws within the scope of the claims of the present application.
Claims (7)
1. An antimicrobial powder coating, characterized by: the material is prepared from the following raw materials in parts by weight: 30-60 parts of modified acrylic resin, 20-30 parts of modified barium sulfate and 30-60 parts of epoxy resin; 2-8 parts of curing agent; 1-5 parts of dispersing agent; the modified barium sulfate is prepared from the following raw materials: barium sulfate, diethylene glycol dimethyl ether, DOPO, vinyltrimethoxysilane, azobisisobutyronitrile; the preparation method of the modified barium sulfate comprises the following steps: mixing and stirring 40-80 parts by weight of diethylene glycol dimethyl ether and 40-60 parts by weight of DOPO, heating, adding 20-30 parts by weight of vinyltrimethoxysilane and 0.1-0.5 part by weight of azodiisobutyronitrile, mixing and stirring, washing, filtering, adding 30-50 parts by weight of barium sulfate and 80-120 parts by weight of methanol, heating for reaction, filtering to remove solvent, drying, grinding into powder, and obtaining the modified barium sulfate; the preparation method of the modified acrylic resin comprises the following steps: heating 15-45 parts by weight of polybutylene adipate glycol, 8-16 parts by weight of trimethylolpropane and 10-20 parts by weight of 1, 4-butanediol to melt, cooling and stirring, adding 20-60 parts by weight of acrylic resin, 40-60 parts by weight of 2, 2-dimethylolpropionic acid and 15-25 parts by weight of N, N-dimethylformamide, continuously heating and stirring, sequentially adding 20-30 parts by weight of dibromodimethylhydantoin, 30-50 parts by weight of triethylamine and 0.5-1.5 parts by weight of antioxidant, mixing and stirring, washing and drying to obtain the modified acrylic resin; the acrylic resin is Han Hua S-70.
2. An antimicrobial powder coating according to claim 1, wherein: the weight ratio of DOPO, vinyl trimethoxy silane and barium sulfate is 1: (0.42-0.48): (0.84-0.96).
3. An antimicrobial powder coating according to claim 1, wherein: the weight ratio of the polybutylene adipate glycol, the acrylic resin, the 2, 2-dimethylolpropionic acid and the dibromodimethylhydantoin is (0.9-1.05): 1: (1.05-1.2): (0.6-0.7).
4. An antimicrobial powder coating according to claim 1, wherein: the weight ratio of the modified acrylic ester, the modified barium sulfate and the epoxy resin is (1.2-1.4): (0.55-0.65): 1.
5. an antimicrobial powder coating according to claim 1, wherein: the curing agent is beta-hydroxyalkylamide.
6. An antimicrobial powder coating according to claim 1, wherein: the dispersing agent is microcrystalline paraffin.
7. A preparation method of an antibacterial powder coating is characterized by comprising the following steps: an antimicrobial powder coating for use in preparing the antimicrobial powder coating of any one of claims 1-6, comprising the steps of: heating and uniformly mixing epoxy resin, modified barium sulfate and modified acrylic resin, extruding and granulating; adding a curing agent and a dispersing agent, extruding, granulating, tabletting, crushing and screening to obtain the powder coating.
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