CN116535914A - Wear-resistant antibacterial coating and preparation method thereof - Google Patents
Wear-resistant antibacterial coating and preparation method thereof Download PDFInfo
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- CN116535914A CN116535914A CN202310462546.8A CN202310462546A CN116535914A CN 116535914 A CN116535914 A CN 116535914A CN 202310462546 A CN202310462546 A CN 202310462546A CN 116535914 A CN116535914 A CN 116535914A
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- 238000000576 coating method Methods 0.000 title claims abstract description 120
- 239000011248 coating agent Substances 0.000 title claims abstract description 112
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title abstract description 38
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000002071 nanotube Substances 0.000 claims abstract description 108
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 98
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002131 composite material Substances 0.000 claims abstract description 47
- SIQZJFKTROUNPI-UHFFFAOYSA-N 1-(hydroxymethyl)-5,5-dimethylhydantoin Chemical compound CC1(C)N(CO)C(=O)NC1=O SIQZJFKTROUNPI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003973 paint Substances 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000839 emulsion Substances 0.000 claims abstract description 9
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 5
- 239000000440 bentonite Substances 0.000 claims abstract description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 23
- 230000000845 anti-microbial effect Effects 0.000 claims description 22
- 238000005299 abrasion Methods 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 14
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 13
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 239000001038 titanium pigment Substances 0.000 claims description 10
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 9
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 20
- 238000012360 testing method Methods 0.000 description 12
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000009385 viral infection Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000011482 antibacterial activity assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
Classifications
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- 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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention provides a wear-resistant antibacterial coating and a preparation method thereof, wherein the wear-resistant antibacterial coating comprises the following raw materials in parts by weight: 20-35 parts of acrylic emulsion, 5-15 parts of halloysite nanotube composite material, 1-10 parts of bentonite, 10-30 parts of titanium dioxide and 20-30 parts of water; wherein, the halloysite nanotube composite material is halloysite nanotube loaded 1-hydroxymethyl-5, 5-dimethylhydantoin. The wear-resistant antibacterial paint provided by the invention has the advantages of good antibacterial effect and long antibacterial time, and meets the requirements of people on the antibacterial paint.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a wear-resistant antibacterial coating and a preparation method thereof.
Background
Along with the rapid development of economy and the progress of modern science and technology, the requirements of the coating industry on the coating are also high in water fluctuation, and the wear resistance of the coating is especially emphasized, so that the durability and the service life of the coating are directly influenced. The wear resistant coating is applied to the substrate in an attempt to prevent mechanical damage that may lead to surface defects, thereby reducing or eliminating wear and thereby extending the useful life of the coating and substrate.
In addition, various viruses and bacteria exist in the environment, particularly places with more people such as hospitals and markets, the virus and bacteria content is higher, and people can easily cause bacteria or virus infection when contacting the polluted surface, particularly for some special people with poor resistance, the situation that bacteria or virus infection is more likely to occur after contacting the polluted surface of hands. The existing antibacterial paint is prepared by adding an antibacterial agent with an antibacterial function into the paint and processing the paint by a certain process. However, the existing commercial antibacterial paint has short effective antibacterial and bactericidal action time and is easy to pollute the environment.
Based on the above, development of a coating with good wear resistance and long-acting antibacterial property is a problem to be solved at present.
Disclosure of Invention
In order to solve the problems and the defects in the prior art, the invention provides the wear-resistant antibacterial paint and the preparation method thereof, so as to further optimize the wear resistance and antibacterial durability of the paint and meet the requirements of people on the antibacterial paint.
According to one aspect of the invention, there is provided a wear-resistant antibacterial paint comprising the following raw materials in parts by weight: 20-35 parts of acrylic emulsion, 5-15 parts of halloysite nanotube composite material, 1-10 parts of bentonite, 10-30 parts of titanium dioxide and 20-30 parts of water; wherein, the halloysite nanotube composite material is halloysite nanotube loaded 1-hydroxymethyl-5, 5-dimethylhydantoin.
According to the halloysite nanotube composite material in the paint, the halloysite nanotube is loaded with the antibacterial agent 1-hydroxymethyl-5, 5-dimethylhydantoin (3-methyl-5, 5-dimethyl hydantoion, MDMH), and the halloysite nanotube has a special tubular structure, so that the halloysite nanotube has positive charges in the tube and negative charges outside the tube, and therefore the MDMH can be loaded, the MDMH in the paint can be slowly released, the antibacterial time of the MDMH in the paint can be effectively prolonged, and the wear-resistant antibacterial paint using the halloysite nanotube composite material has the advantages of good antibacterial effect and long antibacterial time. Secondly, the titanium dioxide and halloysite nanotube composite materials are matched with each other, so that a synergistic effect can be achieved, and the wear resistance of the wear-resistant antibacterial paint is enhanced.
Preferably, in the halloysite nanotube composite material, the mass ratio of the 1-hydroxymethyl-5, 5-dimethylhydantoin to the halloysite nanotubes is 1-2:1.
The feeding mass ratio of the MDMH to the halloysite nanotube is controlled to be 1-2: 1, thereby increasing the MDMH load in the halloysite nanotube composite material, and releasing the MDMH at a moderate speed, so that the effective antibacterial action time of the wear-resistant antibacterial coating applying the halloysite nanotube composite material is prolonged. If the feeding mass ratio of MDMH to halloysite nanotubes is too small, the effective antibacterial components which can be loaded by the halloysite nanotubes are too small, so that the long-term antibacterial effect of the coating is not facilitated; if the feeding mass ratio of MDMH to halloysite nanotubes is too large, the halloysite nanotubes cannot load excessive MDMH, and the halloysite nanotube composite material prepared by the method is easy to release MDMH in a short period and is unfavorable for long-term release of MDMH.
Preferably, the halloysite nanotube composite is prepared by the following steps: s1, carrying out acid liquor modification treatment on halloysite nanotubes to obtain modified halloysite nanotubes; s2, uniformly mixing the modified halloysite nanotube and 1-hydroxymethyl-5, 5-dimethylhydantoin, stirring for 40-60 minutes in a vacuum environment, and stirring for 10-20 minutes under 0.09-0.11 MPa to obtain the halloysite nanotube composite material.
The inner diameter of the halloysite nanotube is enlarged through modification of the halloysite nanotube, so that the MDMH loadable amount of the halloysite nanotube composite material is increased. The halloysite nanotube composite material prepared by using special preparation conditions has high MDMH load and moderate release speed.
Preferably, the modified halloysite nanotubes have an average outer diameter of 60 to 80nm and an average inner diameter of 30 to 40nm.
Preferably, the titanium dioxide is modified titanium dioxide with the surface being treated by zirconium phosphate coating.
Compared with unmodified titanium dioxide, the modified titanium dioxide with the surface treated by zirconium phosphate coating has good dispersibility in the coating, so that the coating using the modified titanium dioxide has higher storage stability. In addition, the modified titanium dioxide also has certain flame retardant capability, and as zirconium phosphate coated on the surface can be mutually crosslinked during high-temperature combustion, a fireproof barrier is formed, and the transmission of combustible gas, oxygen and heat can be blocked. The modified titanium dioxide is used as a filling material to be added into the coating, so that the covering power and durability of the coating to a matrix can be improved, and a certain research and development potential exists in the aspect of flame retardance.
Preferably, the modified titanium dioxide is prepared by the following steps: uniformly mixing titanium dioxide, water and a dispersing agent, grinding and dispersing to obtain pre-cured slurry with the slurry concentration of 300-350 g/L, uniformly mixing the pre-cured slurry with zirconium sulfate and disodium hydrogen phosphate, and curing for 30-40 min at 45-50 ℃ to obtain the modified titanium dioxide.
The titanium dioxide, the zirconium sulfate solution and the disodium hydrogen phosphate solution react to form a stable zirconium phosphate coating on the surface of the titanium dioxide, and the modified titanium dioxide with the zirconium phosphate uniform coating on the surface can be prepared by the preparation method.
Preferably, in the process of preparing the modified titanium dioxide, the feeding mole ratio of zirconium sulfate to disodium hydrogen phosphate is 1:2 to 2.5.
Preferably, the average tube length of the halloysite nanotubes is 0.5-1 mu m, and the average particle size of the titanium dioxide is 300-350 nm; the mass ratio of the halloysite nanotube composite material to the titanium dioxide is 1:2 to 2.5.
According to the scheme, the feeding mass ratio of the halloysite nanotube to the titanium dioxide and the particle size of the halloysite nanotube to the titanium dioxide are adjusted, so that the dispersibility of the halloysite nanotube and the titanium dioxide in the coating is effectively improved, the possibility that the halloysite nanotube and the titanium dioxide are aggregated to form a lump in the storage and use processes is reduced, and the storage stability of the wear-resistant antibacterial coating is further improved. And when the average particle diameter of the modified titanium dioxide is 300-350 nm, the modified titanium dioxide also has a certain bactericidal effect. The modified titanium dioxide can destroy the integrity of cell membranes of microorganisms and simultaneously cause leakage of cell contents, so that growth and propagation of the microorganisms are inhibited, and the sterilizing and antibacterial effects are achieved.
Preferably, the raw materials for preparing the wear-resistant antibacterial paint also comprise 3-8 parts of pigment, 1-2 parts of dispersing agent, 0.5-2 parts of defoaming agent, 0.5-1 part of flatting agent, 1-2 parts of anti-settling agent and 1-2 parts of wetting agent.
According to a second aspect of the present invention, there is provided a method for preparing the above-mentioned abrasion-resistant antibacterial paint, characterized by comprising the steps of: uniformly mixing the acrylic emulsion, the halloysite nanotube composite material and water to obtain a coating intermediate, and uniformly mixing the coating intermediate with the rest raw materials to obtain the wear-resistant antibacterial coating.
The wear-resistant antibacterial coating provided by the scheme is simple in preparation process, convenient to operate and good in economic benefit.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
The preparation method of the wear-resistant antibacterial paint comprises the following steps:
(1) Preparation of halloysite nanotube composite
The halloysite nanotube composite material provided by the embodiment is prepared by the following steps:
s1, carrying out acid liquor modification treatment on halloysite nanotubes, uniformly mixing the halloysite nanotubes with 1.0mol/L sulfuric acid, and stirring at 80 ℃ for 30 hours to obtain modified halloysite nanotubes. Wherein, the average external diameter of the prepared modified halloysite nanotube is 70nm, and the average internal diameter is 35nm.
S2, uniformly mixing the modified halloysite nanotube and 1-hydroxymethyl-5, 5-dimethylhydantoin, stirring for 50 minutes in a vacuum environment, stirring for 15 minutes under 0.10MPa, washing, filtering and drying at high temperature to obtain the halloysite nanotube composite material. Wherein, the feeding mass ratio of the 1-hydroxymethyl-5, 5-dimethylhydantoin to the modified halloysite nanotube is 2:1.
(2) Preparation of modified titanium dioxide
The modified titanium dioxide provided by the embodiment is prepared by the following steps:
mixing titanium dioxide with water to prepare titanium dioxide slurry with the slurry concentration of 500-700 g/L; and then uniformly mixing the titanium dioxide slurry with a dispersing agent and desalted water, and grinding and dispersing. Diluting the ground and dispersed titanium dioxide slurry to a pre-cured slurry with the concentration of 300-350 g/L by desalted water, uniformly mixing the pre-cured slurry with zirconium sulfate and disodium hydrogen phosphate, and curing for 30-40 min at 45-50 ℃ to coat a layer of zirconium phosphate film on the surface of the titanium dioxide. After curing, regulating the pH value of the system to 6.5-7.5, washing with desalted water, and drying to obtain the modified titanium dioxide.
In the process of preparing the modified titanium dioxide, the feeding mole ratio of zirconium sulfate to disodium hydrogen phosphate is 1:2.
(3) Preparation of wear-resistant antibacterial paint
The wear-resistant antibacterial coating provided by the embodiment comprises the following raw materials in parts by weight: 27 parts of acrylic emulsion, 10 parts of halloysite nanotube composite material prepared in the step (1), 8 parts of bentonite, 20 parts of modified titanium dioxide prepared in the step (2) and 25 parts of water. Wherein, the average tube length of the halloysite nanotube is 0.8 mu m, and the average particle diameter of the modified titanium dioxide is 325nm; the charging mass ratio of the halloysite nanotube composite material to the modified titanium dioxide is 1:2.
preparing materials according to the raw material formula, and preparing the wear-resistant antibacterial paint according to the following steps: uniformly mixing the acrylic emulsion, the halloysite nanotube composite material and water to obtain a coating intermediate, and uniformly mixing the coating intermediate with the rest raw materials to obtain the wear-resistant antibacterial coating.
In the preparation process of the wear-resistant antibacterial coating, pigment, dispersing agent, defoaming agent, leveling agent, anti-settling agent and wetting agent can be added appropriately according to actual conditions.
Example 2
This example refers to the method for preparing a wear-resistant antimicrobial coating provided in example 1, and a wear-resistant antimicrobial coating is prepared, which differs from example 1 in that: in the process of preparing the halloysite nanotube composite material, the feeding mass ratio of the 1-hydroxymethyl-5, 5-dimethylhydantoin to the halloysite nanotube is 1:2. The proportions of the other raw materials and the preparation method are strictly consistent with those of the example 1.
Example 3
This example refers to the method for preparing a wear-resistant antimicrobial coating provided in example 1, and a wear-resistant antimicrobial coating is prepared, which differs from example 1 in that: in the process of preparing the halloysite nanotube composite material, the feeding mass ratio of the 1-hydroxymethyl-5, 5-dimethylhydantoin to the halloysite nanotube is 3:1. The proportions of the other raw materials and the preparation method are strictly consistent with those of the example 1.
Example 4
This example refers to the method for preparing a wear-resistant antimicrobial coating provided in example 1, and a wear-resistant antimicrobial coating is prepared, which differs from example 1 in that: the step of preparing the modified titanium dioxide is omitted, and in the process of preparing the wear-resistant antibacterial paint, the same amount of unmodified titanium dioxide is adopted to replace the modified titanium dioxide. The proportions of the other raw materials and the preparation method are strictly consistent with those of the example 1.
Example 5
This example refers to the method for preparing a wear-resistant antimicrobial coating provided in example 1, and a wear-resistant antimicrobial coating is prepared, which differs from example 1 in that: in the process of preparing the modified titanium dioxide, the feeding mole ratio of zirconium sulfate to disodium hydrogen phosphate is 1:1. the proportions of the other raw materials and the preparation method are strictly consistent with those of the example 1.
Example 6
This example refers to the method for preparing a wear-resistant antimicrobial coating provided in example 1, and a wear-resistant antimicrobial coating is prepared, which differs from example 1 in that: in the process of preparing the modified titanium dioxide, the feeding mole ratio of zirconium sulfate to disodium hydrogen phosphate is 1:3. the proportions of the other raw materials and the preparation method are strictly consistent with those of the example 1.
Example 7
This example refers to the method for preparing a wear-resistant antimicrobial coating provided in example 1, and a wear-resistant antimicrobial coating is prepared, which differs from example 1 in that: in the process of preparing the wear-resistant antibacterial paint, halloysite nanotubes with average tube length of 1.5 mu m and titanium dioxide with average particle size of 400nm are selected, and the feeding mass ratio of the halloysite nanotube composite material to the modified titanium dioxide is adjusted to be 1:1.5. the proportions of the other raw materials and the preparation method are strictly consistent with those of the example 1.
Example 8
This example refers to the method for preparing a wear-resistant antimicrobial coating provided in example 1, and a wear-resistant antimicrobial coating is prepared, which differs from example 1 in that: in the process of preparing the wear-resistant antibacterial paint, halloysite nanotubes with the average tube length of 0.4 mu m and titanium dioxide with the average particle size of 250nm are selected, and the feeding mass ratio of the halloysite nanotube composite material to the modified titanium dioxide is adjusted to be 1:3. the proportions of the other raw materials and the preparation method are strictly consistent with those of the example 1.
Comparative example 1
This comparative example, which is different from example 1 in that a wear-resistant antibacterial paint was prepared with reference to the preparation method provided in example 1: in the embodiment, the preparation step of the halloysite nanotube composite material is omitted, the halloysite nanotube is not contained in the preparation raw materials of the wear-resistant antibacterial coating, and the 1-hydroxymethyl-5, 5-dimethylhydantoin is directly introduced into the coating in a physical mixing mode. The proportions of the other raw materials and the preparation method are strictly consistent with those of the example 1.
Comparative example 2
This comparative example, which is different from example 1 in that a wear-resistant antibacterial paint was prepared with reference to the preparation method provided in example 1: in the embodiment, the preparation step of the halloysite nanotube composite material is omitted, the preparation raw material of the wear-resistant antibacterial coating does not contain 1-hydroxymethyl-5, 5-dimethylhydantoin, and the halloysite nanotube is directly introduced into the coating in a physical mixing mode. The proportions of the other raw materials and the preparation method are strictly consistent with those of the example 1.
Comparative example 3
This comparative example was prepared by referring to the preparation method provided in example 1, and the kind of raw materials used in this comparative example was the same as that used in example 1 for preparing the abrasion-resistant antibacterial coating.
(1) The preparation step of the halloysite nanotube composite material is omitted in the comparative example, so that the preparation raw materials 1-hydroxymethyl-5, 5-dimethylhydantoin and halloysite nanotubes of the halloysite nanotube composite material are directly introduced into the coating in a physical mixing mode, and the specific physical mixing step is shown in the step (3).
(2) Preparation of modified titanium dioxide
This procedure and the raw material composition were exactly the same as in example 1.
(3) Preparation of wear-resistant antibacterial paint
The wear-resistant antibacterial coating provided by the comparative example comprises the following raw materials in parts by weight: 27 parts of acrylic emulsion, 8 parts of bentonite, 20 parts of the modified titanium dioxide prepared in the step (2) and 25 parts of water; the raw materials also comprise 1-hydroxymethyl-5, 5-dimethylhydantoin and halloysite nanotubes, and the feeding amount of the raw materials is consistent with the content of the 1-hydroxymethyl-5, 5-dimethylhydantoin and halloysite nanotubes in the wear-resistant antibacterial coating prepared in the example 1. Wherein, the average tube length of the halloysite nanotube is 0.8 mu m, and the average particle diameter of the modified titanium dioxide is 325nm; the charging mass ratio of the halloysite nanotube composite material to the modified titanium dioxide is 1:2.
preparing materials according to the raw material formula, and preparing the wear-resistant antibacterial paint according to the following steps: uniformly mixing the acrylic emulsion, halloysite nanotube, 1-hydroxymethyl-5, 5-dimethylhydantoin and water to obtain a coating intermediate, and uniformly mixing the coating intermediate with the rest raw materials to obtain the wear-resistant antibacterial coating.
In the preparation process of the wear-resistant antibacterial coating, pigment, dispersing agent, defoaming agent, leveling agent, anti-settling agent and wetting agent can be added appropriately according to actual conditions.
Comparative example 4
This comparative example, which is different from example 1 in that a wear-resistant antibacterial paint was prepared with reference to the preparation method provided in example 1: in the embodiment, the preparation step of the modified titanium dioxide is omitted, and in the preparation process of the wear-resistant antibacterial coating, the modified titanium dioxide is replaced by halloysite nanotubes with equal quantity. The proportions of the other raw materials and the preparation method are strictly consistent with those of the example 1.
Test case
A reference subject: the abrasion-resistant antibacterial coatings provided in examples 1 to 8 and comparative examples 1 to 4.
Test items:
(1) Storage stability: referring to GB/T6753.3-1986 paint storage stability test method, when a distinct settled cake (corresponding to a settlement grade of 8) is detected, the time for the paint of the reference to appear to cake in storage is recorded.
(2) Abrasion resistance: the abrasion resistance of the coating prepared by the reference subject is tested by referring to GB/T23988-2009 abrasion resistance determination method of coating abrasion resistance.
(3) Antibacterial properties, antibacterial durability: referring to GB/T21866-2008 antibacterial paint antibacterial assay and antibacterial Effect, strain selection: staphylococcus aureus (Latin brand name: staphylococcus aureus, AS 1.89), escherichia coli (Latin brand name: escherichia coli, AS 1.90). The antimicrobial properties of the coatings produced by the test subjects were tested.
(4) Fire resistance limit: the flame retardance of the coating obtained by the subject is tested with reference to GB/T9978-2008 method for testing the fire resistance of building elements.
Test results: as shown in table 1.
TABLE 1 test Performance of the test subjects in the test examples
Comparing the test performances of examples 1 to 8 with those of comparative examples 1 to 4 in Table 1, it was found that the abrasion-resistant antibacterial coatings provided in examples 1 to 8 had both excellent abrasion resistance and excellent antibacterial effect. Comparing the test performance of example 1 with that of comparative examples 1 to 3, the coating obtained in example 1 was superior to comparative examples 1 to 3 in both abrasion resistance and antibacterial property, and the coating of example 1 was excellent in storage stability. Comparing the coating of example 1 with the coating of comparative example 1, the coating of example 1 produced a coating having superior abrasion resistance; the coating of example 1 has a higher abrasion resistance and a longer antimicrobial effect than the coating of comparative example 2. Comparing the coating of example 1 with the coating of comparative example 3, the coating of example 1 produced a better antimicrobial effect and a longer-term antimicrobial effect. Therefore, the halloysite nanotube is loaded with the antibacterial agent 1-hydroxymethyl-5, 5-dimethylhydantoin to prepare the halloysite nanotube composite material, and the halloysite nanotube composite material is used for preparing the coating, so that the 1-hydroxymethyl-5, 5-dimethylhydantoin in the coating can be slowly released, the antibacterial time of the 1-hydroxymethyl-5, 5-dimethylhydantoin in the coating can be effectively prolonged, and the wear-resistant antibacterial coating using the halloysite nanotube composite material has the advantages of good antibacterial effect and long antibacterial time.
Comparing the coating of example 1 with the coating of comparative example 4, the coating of example 1 has higher abrasion resistance than the coating of comparative example 4, which can demonstrate that when the abrasion-resistant antimicrobial coating contains titanium pigment and halloysite nanotubes simultaneously, the coating prepared from the coating can exhibit excellent abrasion resistance, i.e., the titanium pigment and the halloysite nanotubes are matched with each other, and can play a synergistic effect, and the abrasion-resistant effect is better than that of the coating corresponding to the coating only added with the halloysite nanotubes.
Comparing the test properties shown in Table 1 for examples 1-3, it was found that the coatings prepared in example 1 had higher antimicrobial properties and longer effective antimicrobial times than the coatings of examples 2-3. Therefore, when the mass ratio of the 1-hydroxymethyl-5, 5-dimethylhydantoin (MDMH) to the halloysite nanotubes in the halloysite nanotube composite material is 1-2:1, the MDMH load in the halloysite nanotube composite material can be increased, and the MDMH can be released at a moderate speed, so that the effective antibacterial action time of the wear-resistant antibacterial coating using the halloysite nanotube composite material is prolonged. In the embodiment 2, the feeding mass ratio of MDMH to halloysite nanotubes is too small, and the effective antibacterial components which can be loaded by the halloysite nanotubes are too small, so that the long-term antibacterial effect of the coating is not facilitated; in example 3, the mass ratio of MDMH to halloysite nanotubes was too large, the halloysite nanotubes could not be loaded with excessive MDMH, and the halloysite nanotube composite material thus prepared easily released MDMH in a short period, which was unfavorable for long-term release of MDMH. In addition, the coatings prepared by the wear-resistant antibacterial coatings of examples 1-3 have better antibacterial performance, and are particularly characterized by having antibacterial performance higher than 99% and antibacterial durability higher than 95%, so that the I-level requirement of the antibacterial coating is met.
Comparing the properties of example 1 with those of example 4 in table 1, the coating prepared in example 1 has excellent storage stability, and the coating prepared in example 1 has good flame retardant effect. Therefore, compared with unmodified titanium dioxide, the modified titanium dioxide with the surface being coated with zirconium phosphate has good dispersibility in the coating, so that the coating using the modified titanium dioxide has higher storage stability. And the paint added with the modified titanium dioxide also has a certain flame-retardant effect. Comparing the properties of example 1 with those of examples 5 to 6 in Table 1, the storage stability of the coating prepared in example 1 is better than that of the coating prepared in examples 5 to 6, and the antibacterial property and flame retardant effect measured by the coating provided in example 1 are better, thus demonstrating that the molar ratio of the zirconium sulfate to the disodium hydrogen phosphate is 1 by adjusting the feeding amount of the zirconium sulfate to the disodium hydrogen phosphate in the process of preparing the modified titanium pigment: 2 to 2.5, can promote the reaction of zirconium sulfate and disodium hydrogen phosphate, so that the yield of the zirconium phosphate which is a reaction product is high, and can coat the surface of titanium pigment. If the feeding molar ratio is too large or too small, the reaction conversion rate of zirconium sulfate and disodium hydrogen phosphate can be influenced.
Comparing the test performance measured in example 1 with that measured in examples 7 to 8, the coating prepared in example 1 has excellent storage stability, and the coating prepared in example 1 has good bactericidal and antibacterial effects. Therefore, when the average tube length of the halloysite nanotubes is 0.5-1 mu m, the average particle size of the titanium dioxide is 300-350 nm; the mass ratio of the halloysite nanotube composite material to the titanium dioxide is 1: 2-2.5, the dispersibility of the halloysite nanotubes and the titanium pigment in the paint can be effectively improved, the halloysite nanotubes and the titanium pigment in the paint are uniformly dispersed, the possibility that the halloysite nanotubes and the titanium pigment are aggregated to form non-dispersible caking is reduced in the storage and use processes, and the storage stability of the prepared wear-resistant antibacterial paint is further improved. And when the average particle diameter of the modified titanium dioxide is 300-350 nm, the modified titanium dioxide also has a certain bactericidal effect, the modified titanium dioxide can destroy the integrity of cell membranes of microorganisms and simultaneously cause leakage of cell contents, so that the growth and propagation of the microorganisms are inhibited, and the bactericidal and antibacterial effects are achieved.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The wear-resistant antibacterial coating is characterized by comprising the following raw materials in parts by weight: 20-35 parts of acrylic emulsion, 5-15 parts of halloysite nanotube composite material, 1-10 parts of bentonite, 10-30 parts of titanium dioxide and 20-30 parts of water; wherein, the halloysite nanotube composite material is halloysite nanotube loaded 1-hydroxymethyl-5, 5-dimethylhydantoin.
2. The abrasion-resistant and antibacterial coating according to claim 1, wherein the mass ratio of the 1-hydroxymethyl-5, 5-dimethylhydantoin to the halloysite nanotubes in the halloysite nanotube composite is 1-2:1.
3. The abrasion-resistant and antibacterial coating according to claim 1, wherein the halloysite nanotube composite is prepared by the following steps:
s1, carrying out acid liquor modification treatment on the halloysite nanotube to obtain a modified halloysite nanotube;
s2, uniformly mixing the modified halloysite nanotube and the 1-hydroxymethyl-5, 5-dimethylhydantoin, stirring for 40-60 minutes in a vacuum environment, and then stirring for 10-20 minutes under the pressure of 0.09-0.11 MPa to obtain the halloysite nanotube composite material.
4. The abrasion-resistant and antibacterial paint according to claim 3, wherein the modified halloysite nanotubes have an average outer diameter of 60 to 80nm and an average inner diameter of 30 to 40nm.
5. The wear-resistant antibacterial coating according to claim 1, wherein the titanium pigment is modified titanium pigment with zirconium phosphate coating treatment on the surface.
6. The wear-resistant antibacterial coating according to claim 5, wherein the modified titanium dioxide is prepared by the following steps: uniformly mixing the titanium dioxide, water and a dispersing agent, grinding and dispersing to obtain a pre-cured slurry with the slurry concentration of 300-350 g/L, uniformly mixing the pre-cured slurry with zirconium sulfate and disodium hydrogen phosphate, and curing for 30-40 min at 45-50 ℃ to obtain the modified titanium dioxide.
7. The abrasion-resistant antibacterial coating according to claim 6, wherein in the process of preparing the modified titanium dioxide, the feeding mole ratio of the zirconium sulfate to the disodium hydrogen phosphate is 1:2 to 2.5.
8. The wear-resistant antibacterial coating according to claim 1, wherein the average tube length of the halloysite nanotubes is 0.5-1 μm, and the average particle size of the titanium pigment is 300-350 nm; the mass ratio of the halloysite nanotube composite material to the titanium dioxide is 1:2 to 2.5.
9. The abrasion-resistant antibacterial coating as claimed in claim 1, further comprising the following raw materials in parts by weight: 3 to 8 parts of pigment, 1 to 2 parts of dispersing agent, 0.5 to 2 parts of defoaming agent, 0.5 to 1 part of leveling agent, 1 to 2 parts of anti-settling agent and 1 to 2 parts of wetting agent.
10. A method of preparing a wear resistant antimicrobial coating according to any one of claims 1 to 9, comprising the steps of: and uniformly mixing the acrylic emulsion, the halloysite nanotube composite material and the water to obtain a coating intermediate, and uniformly mixing the coating intermediate with the rest raw materials to obtain the wear-resistant antibacterial coating.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1190422A (en) * | 1995-07-13 | 1998-08-12 | 美国3M公司 | Coatable biocidal composition |
| CN108659641A (en) * | 2018-04-27 | 2018-10-16 | 陈艳琳 | A kind of antibiotic paint |
| CN112715818A (en) * | 2021-02-08 | 2021-04-30 | 江南大学 | Halloysite nanotube-loaded carvacrol sustained-release compound and preparation method thereof |
| CN113563739A (en) * | 2021-07-29 | 2021-10-29 | 安徽金星钛白（集团）有限公司 | Preparation method of composite coated titanium dioxide for bactericidal coating |
| CN114085591A (en) * | 2021-11-16 | 2022-02-25 | 湖南华菱线缆股份有限公司 | High-adhesion mildew-resistant coating for cables |
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2023
- 2023-04-26 CN CN202310462546.8A patent/CN116535914A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1190422A (en) * | 1995-07-13 | 1998-08-12 | 美国3M公司 | Coatable biocidal composition |
| CN108659641A (en) * | 2018-04-27 | 2018-10-16 | 陈艳琳 | A kind of antibiotic paint |
| CN112715818A (en) * | 2021-02-08 | 2021-04-30 | 江南大学 | Halloysite nanotube-loaded carvacrol sustained-release compound and preparation method thereof |
| CN113563739A (en) * | 2021-07-29 | 2021-10-29 | 安徽金星钛白（集团）有限公司 | Preparation method of composite coated titanium dioxide for bactericidal coating |
| CN114085591A (en) * | 2021-11-16 | 2022-02-25 | 湖南华菱线缆股份有限公司 | High-adhesion mildew-resistant coating for cables |
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