CN116751505A - Water-based weather-resistant antibacterial coiled material coating and preparation method thereof - Google Patents
Water-based weather-resistant antibacterial coiled material coating and preparation method thereof Download PDFInfo
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- CN116751505A CN116751505A CN202310771060.2A CN202310771060A CN116751505A CN 116751505 A CN116751505 A CN 116751505A CN 202310771060 A CN202310771060 A CN 202310771060A CN 116751505 A CN116751505 A CN 116751505A
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- 239000000463 material Substances 0.000 title claims abstract description 90
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 85
- 238000000576 coating method Methods 0.000 title claims abstract description 84
- 239000011248 coating agent Substances 0.000 title claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920003180 amino resin Polymers 0.000 claims abstract description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 61
- 229920001225 polyester resin Polymers 0.000 claims abstract description 59
- 239000004645 polyester resin Substances 0.000 claims abstract description 59
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 46
- 239000002114 nanocomposite Substances 0.000 claims abstract description 45
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 43
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003381 stabilizer Substances 0.000 claims abstract description 40
- 229920001709 polysilazane Polymers 0.000 claims abstract description 37
- 239000007822 coupling agent Substances 0.000 claims abstract description 32
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 27
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 25
- VDNSGQQAZRMTCI-UHFFFAOYSA-N sulfanylidenegermanium Chemical compound [Ge]=S VDNSGQQAZRMTCI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims abstract description 16
- 239000003899 bactericide agent Substances 0.000 claims description 45
- 239000002270 dispersing agent Substances 0.000 claims description 45
- 239000002562 thickening agent Substances 0.000 claims description 45
- 239000000080 wetting agent Substances 0.000 claims description 45
- 239000002518 antifoaming agent Substances 0.000 claims description 44
- 239000003795 chemical substances by application Substances 0.000 claims description 41
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- -1 polyoxypropylene Polymers 0.000 claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 12
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical group O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- 229920001451 polypropylene glycol Polymers 0.000 claims description 12
- 229920002635 polyurethane Polymers 0.000 claims description 12
- 239000004814 polyurethane Substances 0.000 claims description 12
- 159000000000 sodium salts Chemical class 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 125000003827 glycol group Chemical group 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 229920005646 polycarboxylate Polymers 0.000 claims description 11
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 10
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 10
- 239000010410 layer Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002356 single layer Substances 0.000 claims description 8
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 claims description 6
- KHOQACYSPZJFSY-UHFFFAOYSA-N CC(C)(C)OC([SiH3])=C(OC(C)(C)C)OC(C)(C)C Chemical compound CC(C)(C)OC([SiH3])=C(OC(C)(C)C)OC(C)(C)C KHOQACYSPZJFSY-UHFFFAOYSA-N 0.000 claims description 6
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 5
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 5
- CIOXFKGQNIJXKF-UHFFFAOYSA-N tris(2-methoxyethoxy)silane Chemical compound COCCO[SiH](OCCOC)OCCOC CIOXFKGQNIJXKF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 abstract description 14
- 230000032683 aging Effects 0.000 abstract description 13
- 239000003513 alkali Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 241000700605 Viruses Species 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 2
- 229910007991 Si-N Inorganic materials 0.000 description 2
- 229910006294 Si—N Inorganic materials 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000009736 wetting Methods 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; 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
- 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
- C08K2003/2231—Oxides; Hydroxides of metals of tin
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
- C08K2003/3027—Sulfides of cadmium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plant Pathology (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to a water-based weather-proof antibacterial coiled material coating and a preparation method thereof; the coating is prepared from the following raw materials: modified polyester resin, amino resin, inorganic polysilazane, photosensitive material, tin oxide/graphene nanocomposite, nano titanium dioxide, coupling agent, stabilizer, auxiliary agent and water; the modified polyester resin is allylated hydroxyl-terminated polybutadiene modified polyester resin; the amino resin is a mixture of fully methylated amino resin and partially methylated amino resin with the mass ratio of 1-3:1; the cadmium sulfide and/or germanium sulfide, the tin oxide/graphene nano compound and the nano titanium dioxide form a stable system which is uniformly dispersed with the modified polyester resin, the amino resin and the inorganic polysilazane through a coupling agent and a stabilizer, and the cured coating shows excellent acid and alkali resistance, water resistance, high and low temperature resistance, ageing resistance and antibacterial property.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a water-based weather-resistant antibacterial coiled material coating and a preparation method thereof.
Background
The coiled material coating is a professional coating used for coating the surfaces of steel plates and aluminum plates and preparing precoated coiled materials, and various functional coiled material coatings, such as fireproof heat-insulating coiled material coating, low-temperature curing coiled material coating, anti-corrosion heat-insulating coiled material coating, VHP (very high-temperature oxidation) resistant coiled material coating, anti-static coiled material coating, antibacterial clean coiled material coating and the like, are developed according to different use environments of coiled materials, and the coiled material coating with specific functions is selected according to specific use environments.
In northern areas of China, most coiled materials are outdoor color steel tiles, when the coiled materials are used as the color steel tiles, the service life of the coiled materials is reduced due to the external environment effects of acid medium erosion, wind, sun, rain and the like, and aiming at the problem, the development of the coiled material coating with good weather resistance, ageing resistance and antibacterial property is necessary.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a water-based weather-resistant antibacterial coiled material coating and a preparation method thereof.
The purpose of the invention is realized in the following way:
the water-based weather-proof antibacterial coiled material coating is prepared from the following raw materials: modified polyester resin, amino resin, inorganic polysilazane, photosensitive material, tin oxide/graphene nanocomposite, nano titanium dioxide, coupling agent, stabilizer, auxiliary agent and water;
the modified polyester resin is allylated hydroxyl-terminated polybutadiene modified polyester resin;
the amino resin is a mixture of fully methylated amino resin and partially methylated amino resin in the mass ratio of 1-3:1.
The invention has the following effective effects: the modified polyester resin contains-CH=CH-, -COOC-, -OH, -COOH active functional groups, -CH2OH, -NH, -CH 2OCH3 active functional groups in amino resin and Si-N active functional groups of inorganic polysilazane which are mutually crosslinked to form a crosslinked polymer containing melamine skeleton, allylated hydroxyl-terminated polybutadiene molecular chain and Si-O bond, residual active functional groups which do not participate in reaction are self-crosslinked between molecules, and the mutual crosslinking and self-crosslinking products are mutually crosslinked to cooperate to finally form a very compact inorganic-organic coating film, so that the coating layer can finally show excellent water resistance, acid and alkali resistance, high and low temperature resistance and ageing resistance, and can jointly play the unique effects of compounding the organic polymer and inorganic silicon oxide, so that the coating film has stronger resistance capability and can prolong the service life by about 3-5 years when suffering from external complex environment change.
Preferably, the photosensitive material is any one or a mixture of two of cadmium sulfide and germanium sulfide.
Preferably, the graphene in the tin oxide/graphene nanocomposite has a lamellar structure of 3 layers or less.
Preferably, the particle size of the nano titanium dioxide is 10-100 nm.
Preferably, the coupling agent is any one or more of tri-tert-butoxyvinylsilane, gamma- (beta-aminoethyl) aminopropyl trimethoxysilane, gamma-methacryloxypropyl tris (beta-methoxyethoxy) silane or gamma-isocyanatopropyl trimethoxysilane;
the stabilizer is one or more of benzyl triethyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium bisulfate, trioctyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride;
the auxiliary agent is one or more of wetting agent, dispersing agent, defoaming agent, antifreezing agent, bactericide and thickener.
Preferably, the wetting agent is alkylphenol ethoxylate, the dispersing agent is polycarboxylate sodium salt, the defoaming agent is glycerol polyoxypropylene ether, the antifreezing agent is glycol, the bactericide is isothiazolinone, and the thickening agent is polyether polyurethane.
Preferably, the coating comprises the following raw materials in parts by weight: 40-55 parts of modified polyester resin, 5-10 parts of amino resin, 5-8 parts of inorganic polysilazane, 5-10 parts of photosensitive material, 3-5 parts of tin oxide/graphene nano-composite, 2-5 parts of nano titanium dioxide, 0.2-2 parts of coupling agent, 0.5-2 parts of stabilizer, 0.5-2 parts of auxiliary agent and 1-38.8 parts of water.
Preferably, the auxiliary agent comprises the following raw materials in parts by weight: 0.1 to 0.4 part of wetting agent, 0.1 to 0.5 part of dispersing agent, 0.1 to 0.2 part of defoaming agent, 0 to 1 part of antifreezing agent, 0.1 to 0.5 part of bactericide and 0.1 to 0.5 part of thickening agent.
Preferably, the coating comprises the following raw materials in parts by weight: 50 parts of modified polyester resin, 5 parts of amino resin, 5 parts of inorganic polysilazane, 10 parts of photosensitive material, 5 parts of tin oxide/graphene nanocomposite, 5 parts of nano titanium dioxide, 2 parts of coupling agent, 2 parts of stabilizer, 2 parts of auxiliary agent and 14 parts of water;
the amino resin is a mixture of fully methylated amino resin and partially methylated amino resin in a mass ratio of 2:1; the graphene in the tin oxide/graphene nano-composite is of a single-layer lamellar structure, and the photosensitive material is a mixture of cadmium sulfide and germanium sulfide with the mass of 1:1; the auxiliary agent comprises the following raw materials in parts by weight: 0.2 part of wetting agent, 0.2 part of dispersing agent, 0.1 part of defoaming agent, 0.6 part of antifreezing agent, 0.5 part of bactericide and 0.4 part of thickening agent.
The invention discloses a preparation method of a water-based weather-proof antibacterial coiled material coating, which comprises the following steps:
step 1: uniformly mixing a wetting agent, a dispersing agent, a defoaming agent and water, and stirring for 2-5 min at the rotating speed of 300-700 r/min;
step 2: the rotating speed is adjusted from 300 r/min to 700r/min to 2000 r/min to 2400r/min, the photosensitive material, the tin oxide/graphene nano-composite and the nano-titanium dioxide are sequentially added, and stirring is continued for 10min to 30min;
step 3: and after the continuous stirring is finished, adding modified polyester resin, amino resin, inorganic polysilazane, a stabilizer, an antifreezing agent, a bactericide and a thickener, and then stirring again until the viscosity is 85-95 KU.
According to the water-based weather-resistant antibacterial coiled material coating and the preparation method thereof, the modified polyester resin is modified by using allylated hydroxyl-terminated polybutadiene as a modifier, and has the same performance as that of solid rubber, so that the modified polyester resin has excellent hydrolysis resistance, acid-base resistance, low temperature resistance, light resistance and other performances, and the defects of high shrinkage rate, low adhesive toughness and the like of the polyester resin are greatly overcome; the amino resin structure used in the invention contains melamine skeleton and a large amount of active alkoxy groups, partial hydroxymethyl and imino groups, so that the amino resin structure has excellent gloss, fullness and hardness, is matched with main resin, and forms a compact coating film through cross-linking and self-crosslinking during curing, thereby showing outstanding chemical resistance, temperature resistance and weather resistance; the inorganic polysilazane can be used as an inorganic binder, has Si-NH-Si bonds, can be cured at room temperature, and has good binding force with a substrate because the reaction in the curing is mainly hydrolysis and oxidation of the Si-NH-Si bonds and the Si-NH-Si bonds are easy to react with-OH on the surface of the substrate; meanwhile, the inorganic polysilazane can promote the reaction of Si-H and Si-NH-Si in the resin, and the resin is solidified to form a compact SiOx coating which is not mixed with H because the SiOx coating belongs to the Si-based inorganic oxide coating + The reaction occurs, so the paint has strong acid resistance, and also has good performances of high and low temperature resistance, light resistance, scratch resistance, stain resistance, water resistance, flame retardance, ultraviolet resistance, ageing resistance and the like; when the coating film of the invention is cured, the modified polyester resinThe preparation method comprises the steps of (1) cross-linking the active functional groups of-CH=CH-, -COOC-, -OH, -COOH, the active functional groups of-CH 2OH, -NH and CH2OCH3 of amino resin and the Si-N active functional groups of inorganic polysilazane to form a cross-linked polymer containing melamine skeleton, allylated hydroxyl-terminated polybutadiene molecular chain and Si-O bond, wherein the residual active functional groups which do not participate in the reaction are subjected to intermolecular or intramolecular self-crosslinking, the cross-crosslinking and the self-crosslinking product are cross-linked mutually to cooperate, so that a very compact inorganic-organic coating film is finally formed, the coating film shows excellent water resistance, acid-base resistance, high temperature resistance and ageing resistance, and the unique compound use effect of the organic polymer and inorganic silicon oxide is jointly exerted, so that the coating film has stronger resistance when suffering from external complex environment change, and the service life is prolonged approximately by 3-5 years; the invention also comprises a photosensitive material, wherein the photosensitive material is preferably high-purity cadmium sulfide and/or germanium sulfide, and the cadmium sulfide and/or the germanium sulfide have strong photoelectric effect on visible light; namely, under the irradiation of light, electrons in the material can be excited by photons to form current, and simultaneously, the current is conducted to all parts of the coating by the aid of the conductive performance of the tin oxide/graphene nanocomposite, bacteria and viruses growing in the coating and bacteria and viruses around the coating are adsorbed and killed, and good antibacterial performance is shown; furthermore, the photochemical performance of the nano titanium dioxide is also used, so that pollutants in the air such as nitrogen oxides, aldehydes and the like can be decomposed, the coating is ensured to be in a good external environment, and the other performances of the coating are favorably exerted; furthermore, cadmium sulfide and/or germanium sulfide in the photosensitive material can absorb most of visible light, nano titanium dioxide resists ultraviolet light in a wave band of 280nm-400nm, and the light resistance of allylated hydroxyl-terminated polybutadiene modified polyester resin and the ultraviolet resistance of inorganic polysilazane are combined, so that the ageing resistance of the coating is effectively improved by the synergistic effect of the components; the cadmium sulfide and/or germanium sulfide, the tin oxide/graphene nano compound and the nano titanium dioxide form a stable system which is uniformly dispersed with the modified polyester resin, the amino resin and the inorganic polysilazane through the coupling agent and the stabilizer, and the coating after curing shows excellent acid resistanceAlkali resistance, water resistance, high and low temperature resistance, ageing resistance and antibacterial property.
Detailed Description
The invention relates to a water-based weather-resistant antibacterial coiled material coating and a preparation method thereof, wherein the coating is prepared from the following raw materials: modified polyester resin, amino resin, inorganic polysilazane, photosensitive material, tin oxide/graphene nanocomposite, nano titanium dioxide, coupling agent, stabilizer, auxiliary agent and water; the modified polyester resin is allylated hydroxyl-terminated polybutadiene modified polyester resin; the amino resin is a mixture of fully methylated amino resin and partially methylated amino resin in the mass ratio of 1-3:1. The photosensitive material is any one or a mixture of two of cadmium sulfide and germanium sulfide. The graphene in the tin oxide/graphene nanocomposite is in a 3-layer and lower-layer structure. The particle size of the nano titanium dioxide is 10-100 nm. The coupling agent is any one or more of tri-tert-butoxyvinylsilane, gamma- (beta-aminoethyl) aminopropyl trimethoxysilane, gamma-methacryloxypropyl tri (beta-methoxyethoxy) silane or gamma-isocyanatopropyl trimethoxysilane; the stabilizer is one or more of benzyl triethyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium bisulfate, trioctyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride; the auxiliary agent is one or more of wetting agent, dispersing agent, defoaming agent, antifreezing agent, bactericide and thickener. The wetting agent is alkylphenol ethoxylate, the dispersing agent is polycarboxylate sodium salt, the defoaming agent is glycerol polyoxypropylene ether, the antifreezing agent is glycol, the bactericide is isothiazolinone, and the thickening agent is polyether polyurethane.
Further, the coating comprises the following raw materials in parts by weight: 40-55 parts of modified polyester resin, 5-10 parts of amino resin, 5-8 parts of inorganic polysilazane, 5-10 parts of photosensitive material, 3-5 parts of tin oxide/graphene nano-composite, 2-5 parts of nano titanium dioxide, 0.2-2 parts of coupling agent, 0.5-2 parts of stabilizer, 0.5-2 parts of auxiliary agent and 1-38.8 parts of water.
Further, the auxiliary agent comprises the following raw materials in parts by weight: 0.1 to 0.4 part of wetting agent, 0.1 to 0.5 part of dispersing agent, 0.1 to 0.2 part of defoaming agent, 0 to 1 part of antifreezing agent, 0.1 to 0.5 part of bactericide and 0.1 to 0.5 part of thickening agent.
Further, the invention discloses an aqueous weather-resistant antibacterial coiled material coating, which is prepared from the following raw materials in parts by weight: 50 parts of modified polyester resin, 5 parts of amino resin, 5 parts of inorganic polysilazane, 10 parts of photosensitive material, 5 parts of tin oxide/graphene nanocomposite, 5 parts of nano titanium dioxide, 2 parts of coupling agent, 2 parts of stabilizer, 2 parts of auxiliary agent and 14 parts of water; the amino resin is a mixture of fully methylated amino resin and partially methylated amino resin in a mass ratio of 2:1; the graphene in the tin oxide/graphene nano-composite is of a single-layer lamellar structure, and the photosensitive material is a mixture of cadmium sulfide and germanium sulfide with the mass of 1:1; the auxiliary agent comprises the following raw materials in parts by weight: 0.2 part of wetting agent, 0.2 part of dispersing agent, 0.1 part of defoaming agent, 0.6 part of antifreezing agent, 0.5 part of bactericide and 0.4 part of thickening agent.
The invention discloses a preparation method of a water-based weather-proof antibacterial coiled material coating, which comprises the following steps:
step 1: uniformly mixing a wetting agent, a dispersing agent, a defoaming agent and water, and stirring for 2-5 min at the rotating speed of 300-700 r/min;
step 2: the rotating speed is adjusted from 300 r/min to 700r/min to 2000 r/min to 2400r/min, the photosensitive material, the tin oxide/graphene nano-composite and the nano-titanium dioxide are sequentially added, and stirring is continued for 10min to 30min;
step 3: and after the continuous stirring is finished, adding modified polyester resin, amino resin, inorganic polysilazane, a stabilizer, an antifreezing agent, a bactericide and a thickener, and then stirring again until the viscosity is 85-95 KU.
The brand of the fully methylated amino resin used in the invention is XA9303J, and the performance indexes are as follows: viscosity is 2000-9800, solid content is more than or equal to 98%, free aldehyde is less than or equal to 0.5%, acid value is less than or equal to 0.5mgKOH/g; the brand of the partially methylated amino resin is XA9303-80, and the performance indexes are as follows: viscosity 2300-9800, solid content 80+ -2%, free aldehyde less than or equal to 1%, acid value less than or equal to 0.5%; the dispersant polycarboxylic acid sodium salt used in the invention is purchased from wetting macro chemical industry Co., ltd, and the model is 5027; the wetting agent is alkylphenol polyoxyethylene which is purchased from Guangzhou Hengyu chemical industry Co., ltd, and the model is PE100; the defoaming agent is glycerol polyoxypropylene ether purchased from Jiangsu province sea-An petrochemical plant, and the model is GP-330; the antifreezing agent is glycol purchased from Shandong Zhengyu chemical technology Co., ltd; the bactericide is isothiazolinone purchased from Kunshanxin environmental protection technology Co., ltd, and the model is SP-301B; the thickener is polyether polyurethane, and is purchased from Guangdong Lisheng Polymer technology Co., ltd, and the model is LS-8W.
The invention will now be further described in connection with specific embodiments for a clearer explanation thereof. Specific examples are as follows:
example 1
The water-based weather-resistant antibacterial coiled material coating is prepared from the following raw materials in parts by weight: 35 parts of modified polyester resin, 12 parts of amino resin, 9 parts of inorganic polysilazane, 4 parts of photosensitive material, 6 parts of tin oxide/graphene nano-composite, 1 part of nano titanium dioxide, 0.8 part of coupling agent, 2.5 parts of stabilizer, 1.5 parts of auxiliary agent and 40 parts of water; the auxiliary agent is prepared from the following raw materials in parts by weight: 0.1 part of wetting agent, 0.6 part of dispersing agent, 0.25 part of defoaming agent, 0.05 part of bactericide and 0.6 part of thickening agent. The modified polyester resin in this example is an allylated hydroxyl-terminated polybutadiene modified polyester resin; the amino resin is a mixture of fully methylated amino resin and partially methylated amino resin in a mass ratio of 1:1. The photosensitive material is cadmium sulfide. The graphene in the tin oxide/graphene nanocomposite is of a 3-layer structure. The particle size of the nano titanium dioxide is 60nm. The coupling agent is tri-tert-butoxyvinylsilane; the stabilizer is tetrabutylammonium bromide; the auxiliary agent comprises a wetting agent, a dispersing agent, a defoaming agent, a bactericide and a thickening agent; the wetting agent is alkylphenol ethoxylate, the dispersing agent is polycarboxylate sodium salt, the defoaming agent is glycerol polyoxypropylene ether, the bactericide is isothiazolinone, and the thickening agent is polyether polyurethane.
Step 1: uniformly mixing a wetting agent, a dispersing agent, a defoaming agent and water, and stirring for 2min at the rotating speed of 300-700 r/min;
step 2: the rotating speed is adjusted from 300 r/min to 700r/min to 2000 r/min to 2400r/min, the photosensitive material, the tin oxide/graphene nano-composite and the nano-titanium dioxide are sequentially added, and stirring is continued for 30min;
step 3: after the stirring is finished, adding the modified polyester resin, the amino resin, the inorganic polysilazane, the stabilizer, the bactericide and the thickener, and then stirring again until the viscosity is 85KU.
Example 2
The water-based weather-resistant antibacterial coiled material coating is prepared from the following raw materials in parts by weight: 40 parts of modified polyester resin, 5 parts of amino resin, 5 parts of inorganic polysilazane, 5 parts of photosensitive material, 3 parts of tin oxide/graphene nano-composite, 2 parts of nano titanium dioxide, 0.2 part of coupling agent, 0.5 part of stabilizer, 0.5 part of auxiliary agent and 1 part of water; the auxiliary agent is prepared from the following raw materials in parts by weight: 0.1 part of wetting agent, 0.1 part of dispersing agent, 0.1 part of defoaming agent, 1 part of antifreezing agent, 0.1 part of bactericide and 0.1 part of thickening agent.
The modified polyester resin in this example is an allylated hydroxyl-terminated polybutadiene modified polyester resin; the amino resin is a mixture of fully methylated amino resin and partially methylated amino resin in a mass ratio of 3:1. The photosensitive material is a mixture of cadmium sulfide and germanium sulfide, and the mass ratio of the cadmium sulfide to the germanium sulfide is 1:1. the graphene in the tin oxide/graphene nanocomposite is of a single-layer structure. The particle size of the nano titanium dioxide is 100nm. The coupling agent is a mixture of tri-tert-butoxyvinylsilane, gamma- (beta-aminoethyl) aminopropyl trimethoxysilane, gamma-methacryloxypropyl tris (beta-methoxyethoxy) silane and gamma-isocyanatopropyl trimethoxysilane; the stabilizer is a mixture of benzyl triethyl ammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride; the auxiliary agent comprises a wetting agent, a dispersing agent, a defoaming agent, an antifreezing agent, a bactericide and a thickening agent; the wetting agent is alkylphenol ethoxylate, the dispersing agent is polycarboxylate sodium salt, the defoaming agent is glycerol polyoxypropylene ether, the antifreezing agent is glycol, the bactericide is isothiazolinone, and the thickening agent is polyether polyurethane.
Step 1: uniformly mixing a wetting agent, a dispersing agent, a defoaming agent and water, and stirring for 5min at a rotating speed of 300-700 r/min;
step 2: the rotating speed is adjusted from 300 r/min to 700r/min to 2000 r/min to 2400r/min, the photosensitive material, the tin oxide/graphene nano-composite and the nano-titanium dioxide are sequentially added, and stirring is continued for 10min;
step 3: and after the stirring is finished, adding modified polyester resin, amino resin, inorganic polysilazane, a stabilizer, an antifreezing agent, a bactericide and a thickener, and then stirring again until the viscosity is 95 KU.
Example 3
The water-based weather-resistant antibacterial coiled material coating is prepared from the following raw materials in parts by weight: 55 parts of modified polyester resin, 10 parts of amino resin, 8 parts of inorganic polysilazane, 10 parts of photosensitive material, 5 parts of tin oxide/graphene nano-composite, 5 parts of nano titanium dioxide, 2 parts of coupling agent, 0.5-2 parts of stabilizer, 2 parts of auxiliary agent and 38.8 parts of water; the auxiliary agent is prepared from the following raw materials in parts by weight: 0.4 part of wetting agent, 0.5 part of dispersing agent, 0.2 part of defoaming agent, 0.5 part of antifreezing agent, 0.5 part of bactericide and 0.5 part of thickening agent.
The modified polyester resin in this example is an allylated hydroxyl-terminated polybutadiene modified polyester resin; the amino resin is a mixture of fully methylated amino resin and partially methylated amino resin in a mass ratio of 2:1. The photosensitive material is germanium sulfide. The graphene in the tin oxide/graphene nanocomposite is of a 2-layer structure. The particle size of the nano titanium dioxide is 10nm. The coupling agent is gamma-isocyanatopropyl trimethoxy silane; the stabilizer is benzyl triethyl ammonium chloride; the auxiliary agent comprises wetting agent, dispersing agent, defoaming agent, antifreezing agent, bactericide and thickening agent; the wetting agent is alkylphenol ethoxylate, the dispersing agent is polycarboxylate sodium salt, the defoaming agent is glycerol polyoxypropylene ether, the antifreezing agent is glycol, the bactericide is isothiazolinone, and the thickening agent is polyether polyurethane.
Step 1: uniformly mixing a wetting agent, a dispersing agent, a defoaming agent and water, and stirring for 4min at a rotating speed of 300-700 r/min;
step 2: the rotating speed is adjusted from 300 r/min to 700r/min to 2000 r/min to 2400r/min, the photosensitive material, the tin oxide/graphene nano-composite and the nano-titanium dioxide are sequentially added, and stirring is continued for 20min;
step 3: and after the continuous stirring is finished, adding modified polyester resin, amino resin, inorganic polysilazane, a stabilizer, an antifreezing agent, a bactericide and a thickener, and then stirring again until the viscosity is 90 KU.
Example 4
The water-based weather-resistant antibacterial coiled material coating is prepared from the following raw materials in parts by weight: 47 parts of modified polyester resin, 8 parts of amino resin, 6 parts of inorganic polysilazane, 8 parts of photosensitive material, 4 parts of tin oxide/graphene nano-composite, 3 parts of nano titanium dioxide, 1.1 parts of coupling agent, 1.3 parts of stabilizer, 1.2 parts of auxiliary agent and 19.9 parts of water; the auxiliary agent is prepared from the following raw materials in parts by weight: 0.3 part of wetting agent, 0.3 part of dispersing agent, 0.15 part of defoamer, 0.6 part of antifreezing agent, 0.3 part of bactericide and 0.3 part of thickener.
The modified polyester resin in this example is an allylated hydroxyl-terminated polybutadiene modified polyester resin; the amino resin is a mixture of fully methylated amino resin and partially methylated amino resin in a mass ratio of 3:1. The photosensitive material is a mixture of cadmium sulfide and germanium sulfide, and the mass ratio of the cadmium sulfide to the germanium sulfide is 2:1. the graphene in the tin oxide/graphene nanocomposite is in a 3-layer and lower-layer structure. The particle size of the nano titanium dioxide is 55nm. The coupling agent is gamma- (beta-aminoethyl) aminopropyl trimethoxysilane; the stabilizer is tetrabutylammonium bisulfate; the auxiliary agent is one or more of wetting agent, dispersing agent, defoaming agent, antifreezing agent, bactericide and thickening agent; the wetting agent is alkylphenol ethoxylate, the dispersing agent is polycarboxylate sodium salt, the defoaming agent is glycerol polyoxypropylene ether, the antifreezing agent is glycol, the bactericide is isothiazolinone, and the thickening agent is polyether polyurethane.
Step 1: uniformly mixing a wetting agent, a dispersing agent, a defoaming agent and water, and stirring for 3min at a rotating speed of 300-700 r/min;
step 2: the rotating speed is adjusted from 300 r/min to 700r/min to 2000 r/min to 2400r/min, the photosensitive material, the tin oxide/graphene nano-composite and the nano-titanium dioxide are sequentially added, and stirring is continued for 18min;
step 3: and after the continuous stirring is finished, adding modified polyester resin, amino resin, inorganic polysilazane, a stabilizer, an antifreezing agent, a bactericide and a thickener, and then stirring again until the viscosity is 88 KU.
Example 5
The water-based weather-resistant antibacterial coiled material coating is prepared from the following raw materials in parts by weight: 50 parts of modified polyester resin, 5 parts of amino resin, 5 parts of inorganic polysilazane, 10 parts of photosensitive material, 5 parts of tin oxide/graphene nanocomposite, 5 parts of nano titanium dioxide, 2 parts of coupling agent, 2 parts of stabilizer, 2 parts of auxiliary agent and 14 parts of water; the amino resin is a mixture of fully methylated amino resin and partially methylated amino resin in a mass ratio of 2:1; the graphene in the tin oxide/graphene nano-composite is of a single-layer lamellar structure, and the photosensitive material is a mixture of cadmium sulfide and germanium sulfide with the mass of 1:1; the auxiliary agent comprises the following raw materials in parts by weight: 0.2 part of wetting agent, 0.2 part of dispersing agent, 0.1 part of defoaming agent, 0.6 part of antifreezing agent, 0.5 part of bactericide and 0.4 part of thickening agent.
The modified polyester resin in this example is an allylated hydroxyl-terminated polybutadiene modified polyester resin; the particle size of the nano titanium dioxide is 40nm. The coupling agent is gamma-isocyanatopropyl trimethoxy silane; the stabilizer is benzyl triethyl ammonium chloride; the auxiliary agent comprises a wetting agent, a dispersing agent, a defoaming agent, an antifreezing agent, a bactericide and a thickening agent; the wetting agent is alkylphenol ethoxylate, the dispersing agent is polycarboxylate sodium salt, the defoaming agent is glycerol polyoxypropylene ether, the antifreezing agent is glycol, the bactericide is isothiazolinone, and the thickening agent is polyether polyurethane.
Step 1: uniformly mixing a wetting agent, a dispersing agent, a defoaming agent and water, and stirring for 4min at a rotating speed of 300-700 r/min;
step 2: the rotating speed is adjusted from 300 r/min to 700r/min to 2000 r/min to 2400r/min, the photosensitive material, the tin oxide/graphene nano-composite and the nano-titanium dioxide are sequentially added, and stirring is continued for 27min;
step 3: and after the continuous stirring is finished, adding modified polyester resin, amino resin, inorganic polysilazane, a stabilizer, an antifreezing agent, a bactericide and a thickener, and then stirring again until the viscosity is 90 KU.
Example 6
The water-based weather-resistant antibacterial coiled material coating is prepared from the following raw materials in parts by weight: 50 parts of modified polyester resin, 5 parts of amino resin, 5 parts of inorganic polysilazane, 10 parts of photosensitive material, 5 parts of tin oxide/graphene nanocomposite, 5 parts of nano titanium dioxide, 2 parts of coupling agent, 2 parts of stabilizer, 2 parts of auxiliary agent and 14 parts of water; the amino resin is a mixture of fully methylated amino resin and partially methylated amino resin in a mass ratio of 2:1; the graphene in the tin oxide/graphene nano-composite is of a single-layer lamellar structure, and the photosensitive material is a mixture of cadmium sulfide and germanium sulfide with the mass of 1:1; the auxiliary agent comprises the following raw materials in parts by weight: 0.2 part of wetting agent, 0.2 part of dispersing agent, 0.1 part of defoaming agent, 0.6 part of antifreezing agent, 0.5 part of bactericide and 0.4 part of thickening agent.
The modified polyester resin in this example is an allylated hydroxyl-terminated polybutadiene modified polyester resin; the particle size of the nano titanium dioxide is 50nm. The coupling agent is trioctyl methyl ammonium chloride; the stabilizer is tetrabutylammonium chloride; the auxiliary agent comprises one or more of wetting agent, dispersing agent, defoaming agent, antifreezing agent, bactericide and thickening agent; the wetting agent is alkylphenol ethoxylate, the dispersing agent is polycarboxylate sodium salt, the defoaming agent is glycerol polyoxypropylene ether, the antifreezing agent is glycol, the bactericide is isothiazolinone, and the thickening agent is polyether polyurethane.
The preparation method in this example is the same as in example 5.
Example 7
The water-based weather-resistant antibacterial coiled material coating is prepared from the following raw materials in parts by weight: 40 parts of modified polyester resin, 6 parts of amino resin, 6 parts of inorganic polysilazane, 8 parts of photosensitive material, 4 parts of tin oxide/graphene nano-composite, 4 parts of nano titanium dioxide, 2 parts of coupling agent, 2 parts of stabilizer, 2 parts of auxiliary agent and 26 parts of water; the amino resin is a mixture of fully methylated amino resin and partially methylated amino resin in a mass ratio of 3:1; the graphene in the tin oxide/graphene nano-composite is of a single-layer lamellar structure, and the photosensitive material is cadmium sulfide; the auxiliary agent comprises the following raw materials in parts by weight: 0.25 part of wetting agent, 0.2 part of dispersing agent, 0.1 part of defoaming agent, 0.5 part of antifreezing agent, 0.65 part of bactericide and 0.3 part of thickening agent. The modified polyester resin in this example is an allylated hydroxyl-terminated polybutadiene modified polyester resin; the particle size of the nano titanium dioxide is 50nm. The coupling agent is gamma-methacryloxypropyl tris (beta-methoxyethoxy) silane; the stabilizer is dodecyl trimethyl ammonium chloride; the auxiliary agent comprises a wetting agent, a dispersing agent, a defoaming agent, an antifreezing agent, a bactericide and a thickening agent; the wetting agent is alkylphenol ethoxylate, the dispersing agent is polycarboxylate sodium salt, the defoaming agent is glycerol polyoxypropylene ether, the antifreezing agent is glycol, the bactericide is isothiazolinone, and the thickening agent is polyether polyurethane.
The preparation method in this example is the same as in example 4.
Example 8
The water-based weather-resistant antibacterial coiled material coating is prepared from the following raw materials in parts by weight: 55 parts of modified polyester resin, 8 parts of amino resin, 6 parts of inorganic polysilazane, 7 parts of photosensitive material, 3 parts of tin oxide/graphene nanocomposite, 4 parts of nano titanium dioxide, 2 parts of coupling agent, 2 parts of stabilizer, 2 parts of auxiliary agent and 11 parts of water; the amino resin is a mixture of fully methylated amino resin and partially methylated amino resin in a mass ratio of 1:1; the graphene in the tin oxide/graphene nano-composite is of a single-layer lamellar structure, and the photosensitive material is cadmium sulfide; the auxiliary agent comprises the following raw materials in parts by weight: 0.2 part of wetting agent, 0.25 part of dispersing agent, 0.1 part of defoaming agent, 0.45 part of antifreezing agent, 0.6 part of bactericide and 0.4 part of thickening agent. The modified polyester resin in this example is an allylated hydroxyl-terminated polybutadiene modified polyester resin; the particle size of the nano titanium dioxide is 25nm. The coupling agent is tri-tert-butoxyvinylsilane; the stabilizer is tetradecyl trimethyl ammonium chloride; the auxiliary agent comprises a wetting agent, a dispersing agent, a defoaming agent, an antifreezing agent, a bactericide and a thickening agent; the wetting agent is alkylphenol ethoxylate, the dispersing agent is polycarboxylate sodium salt, the defoaming agent is glycerol polyoxypropylene ether, the antifreezing agent is glycol, the bactericide is isothiazolinone, and the thickening agent is polyether polyurethane.
The preparation method in this example is the same as in example 3.
The above detailed description is merely for the specific description of the practical embodiments of the invention, and they are not intended to limit the scope of the invention, but all equivalent embodiments, modifications and adaptations which do not depart from the spirit of the invention are intended to be included in the scope of the invention.
Test examples
Sample selection and preparation: the present invention selects examples 5, 6, 7 and 8 as reference groups; comparative example 1 the starting materials, components and preparation process of example 5 were based, except that the amino resin was omitted; comparative example 2 the starting materials, components and preparation process of example 6 were based on the difference that inorganic polysilazane was omitted; comparative example 3 the starting materials, components and preparation method of example 7 were based, except that tin oxide/graphene nanocomposite was omitted; comparative example 4 the starting materials, components and preparation method of example 8 were based on the difference that cadmium sulfide was omitted;
the test process comprises the following steps: the water-based weather-proof and antibacterial coiled material coatings prepared in the examples and the comparative examples are subjected to performance tests, and specifically comprise adhesive force, antibacterial property, artificial aging resistance, boiling water resistance and acid/alkali resistance, wherein the adhesive force is tested according to GB/T6739-2006 standard of a color paint and varnish cross-cut test, and the boiling water resistance, artificial aging resistance and acid/alkali resistance are tested according to T/ZZB 0293-2017 standard of a precoated coiled material coating for building; the antibacterial property is tested according to GB/T1741-2007 standard of mould resistance test method of paint film.
The test results are shown in the following table:
from the above table the following can be concluded: comparative example 1 shows that the coating film has poor boiling water resistance and acid/alkali resistance after the amino resin is omitted, and the amino resin can increase the crosslinking density of the coating film, so that the coating film is more compact; comparative example 2 shows that the inorganic polysilazane cured SiOx inorganic coating film exhibits excellent inorganic characteristics, as shown by the deterioration of the adhesion, boiling water resistance, acid/alkali resistance, and artificial aging resistance of the coating film; comparative example 3 omits SnO 2 The artificial aging resistance and the antibacterial performance of the film coated after the graphene nano composite are poor, which shows that the composite material has a certain amount of absorption effect on light and good transmission effect on current; comparative example 4 shows that the anti-artificial aging and antibacterial properties of the coating film are obviously poor after cadmium sulfide is omitted, and the cadmium sulfide can effectively absorb light and excite electronic activity to form current when being used as a photoelectric material. According to the comparison, the modified polyester resin, the amino resin and the inorganic polysilazane can be compounded to form a very compact inorganic-organic coating, the coating has excellent water resistance, acid and alkali resistance, high and low temperature resistance and ageing resistance, and the unique effects of compounding the organic polymer and the inorganic silicon oxide are exerted together, so that the coating has stronger resistance when the coating is subjected to external complex environment changes; meanwhile, by selecting high-purity cadmium sulfide and/or germanium sulfide as photosensitive materials and matching with the tin oxide/graphene nanocomposite, the current can be conducted to all positions on the basis of forming the current under the irradiation of light, so that the characteristics of adsorbing and killing bacteria and viruses growing inside the coating and bacteria and viruses around the coating are realized; furthermore, the invention also uses the photochemical property of the nano titanium dioxide to decompose pollutants in the air, such as nitrogen oxides, aldehydes and the like, which ensure that the coating is in good external environment and is beneficial to other properties of the coatingBy using cadmium sulfide and/or germanium sulfide, tin oxide/graphene nano-composite and nano titanium dioxide to form a stable system which is uniformly dispersed with modified polyester resin, amino resin and inorganic polysilazane through a coupling agent and a stabilizer, and the cured coating shows excellent acid and alkali resistance, water resistance, high and low temperature resistance, ageing resistance and antibacterial property.
The above detailed description is merely for the specific description of the practical embodiments of the invention, and they are not intended to limit the scope of the invention, but all equivalent embodiments, modifications and adaptations which do not depart from the spirit of the invention are intended to be included in the scope of the invention.
Claims (10)
1. A water-based weather-proof antibacterial coiled material coating is characterized in that: the coating is prepared from the following raw materials: modified polyester resin, amino resin, inorganic polysilazane, photosensitive material, tin oxide/graphene nanocomposite, nano titanium dioxide, coupling agent, stabilizer, auxiliary agent and water;
the modified polyester resin is allylated hydroxyl-terminated polybutadiene modified polyester resin;
the amino resin is a mixture of fully methylated amino resin and partially methylated amino resin in the mass ratio of 1-3:1.
2. The aqueous weather-resistant and antibacterial coil coating as claimed in claim 1, wherein the photosensitive material is any one of cadmium sulfide and germanium sulfide or a mixture of two of them.
3. The aqueous weather resistant and antibacterial coil coating as recited in claim 1, wherein the graphene in the tin oxide/graphene nanocomposite is in a lamellar structure of 3 layers or less.
4. The water-based weather-resistant antibacterial coiled material coating according to claim 1, wherein the particle size of the nano titanium dioxide is 10-100 nm.
5. The water-based weather-resistant antibacterial coiled material coating according to claim 1, wherein the coupling agent is any one or more of tri-tert-butoxyvinylsilane, gamma- (beta-aminoethyl) aminopropyl trimethoxysilane, gamma-methacryloxypropyl tris (beta-methoxyethoxy) silane or gamma-isocyanatopropyl trimethoxysilane;
the stabilizer is one or more of benzyl triethyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium bisulfate, trioctyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride;
the auxiliary agent is one or more of wetting agent, dispersing agent, defoaming agent, antifreezing agent, bactericide and thickener.
6. The water-based weather-resistant antibacterial coiled material coating according to claim 1, wherein the wetting agent is alkylphenol ethoxylate, the dispersing agent is polycarboxylate sodium salt, the defoaming agent is glycerol polyoxypropylene ether, the antifreezing agent is glycol, the bactericide is isothiazolinone, and the thickening agent is polyether polyurethane.
7. The water-based weather-resistant antibacterial coiled material coating according to claim 1, wherein the coating is prepared from the following raw materials in parts by weight: 40-55 parts of modified polyester resin, 5-10 parts of amino resin, 5-8 parts of inorganic polysilazane, 5-10 parts of photosensitive material, 3-5 parts of tin oxide/graphene nano-composite, 2-5 parts of nano titanium dioxide, 0.2-2 parts of coupling agent, 0.5-2 parts of stabilizer, 0.5-2 parts of auxiliary agent and 1-38.8 parts of water.
8. The water-based weather-resistant antibacterial coiled material coating according to claim 7, wherein the auxiliary agent comprises the following raw materials in parts by weight: 0.1 to 0.4 part of wetting agent, 0.1 to 0.5 part of dispersing agent, 0.1 to 0.2 part of defoaming agent, 0 to 1 part of antifreezing agent, 0.1 to 0.5 part of bactericide and 0.1 to 0.5 part of thickening agent.
9. The water-based weather-resistant antibacterial coiled material coating according to claim 8, wherein the coating is prepared from the following raw materials in parts by weight: 50 parts of modified polyester resin, 5 parts of amino resin, 5 parts of inorganic polysilazane, 10 parts of photosensitive material, 5 parts of tin oxide/graphene nanocomposite, 5 parts of nano titanium dioxide, 2 parts of coupling agent, 2 parts of stabilizer, 2 parts of auxiliary agent and 14 parts of water;
the amino resin is a mixture of fully methylated amino resin and partially methylated amino resin in a mass ratio of 2:1; the graphene in the tin oxide/graphene nano-composite is of a single-layer lamellar structure, and the photosensitive material is a mixture of cadmium sulfide and germanium sulfide with the mass of 1:1; the auxiliary agent comprises the following raw materials in parts by weight: 0.2 part of wetting agent, 0.2 part of dispersing agent, 0.1 part of defoaming agent, 0.6 part of antifreezing agent, 0.5 part of bactericide and 0.4 part of thickening agent.
10. The preparation method of the water-based weather-resistant antibacterial coiled material coating is characterized by comprising the following steps of:
step 1: uniformly mixing a wetting agent, a dispersing agent, a defoaming agent and water, and stirring for 2-5 min at the rotating speed of 300-700 r/min;
step 2: the rotating speed is adjusted from 300 r/min to 700r/min to 2000 r/min to 2400r/min, the photosensitive material, the tin oxide/graphene nano-composite and the nano-titanium dioxide are sequentially added, and stirring is continued for 10min to 30min;
step 3: and after the continuous stirring is finished, adding modified polyester resin, amino resin, inorganic polysilazane, a stabilizer, an antifreezing agent, a bactericide and a thickener, and then stirring again until the viscosity is 85-95 KU.
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