CN114656846A - Stainless steel composite functional coating and preparation method thereof - Google Patents
Stainless steel composite functional coating and preparation method thereof Download PDFInfo
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- CN114656846A CN114656846A CN202011539369.1A CN202011539369A CN114656846A CN 114656846 A CN114656846 A CN 114656846A CN 202011539369 A CN202011539369 A CN 202011539369A CN 114656846 A CN114656846 A CN 114656846A
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- 238000000576 coating method Methods 0.000 title claims abstract description 53
- 239000011248 coating agent Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 29
- 239000010935 stainless steel Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- 239000004593 Epoxy Substances 0.000 claims abstract description 23
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 19
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 18
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 12
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 7
- 239000003899 bactericide agent Substances 0.000 claims abstract description 7
- 239000006184 cosolvent Substances 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 7
- 239000002562 thickening agent Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 229920000388 Polyphosphate Polymers 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical group [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 14
- 229920000058 polyacrylate Polymers 0.000 claims description 14
- 239000001205 polyphosphate Substances 0.000 claims description 14
- 235000011176 polyphosphates Nutrition 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 12
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 10
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 10
- WDHYRUBXLGOLKR-UHFFFAOYSA-N phosphoric acid;prop-2-enoic acid Chemical group OC(=O)C=C.OP(O)(O)=O WDHYRUBXLGOLKR-UHFFFAOYSA-N 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 239000010445 mica Substances 0.000 claims description 8
- 229910052618 mica group Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 8
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 7
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 7
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 claims description 6
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 4
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 4
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 4
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 4
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 4
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000003973 paint Substances 0.000 abstract description 4
- 230000003115 biocidal effect Effects 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 230000002155 anti-virotic effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- 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
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- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
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- 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
- C08K3/32—Phosphorus-containing compounds
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- C08K2003/328—Phosphates of heavy metals
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a stainless steel composite functional coating which comprises the following components in percentage by mass: 30-50% of waterborne modified epoxy acrylic resin; 5-20% of silicon-zirconium nano sol with the particle size of 15-30 nm; 10-20% of filler; 30-60% of deionized water; 0.2 to 1.5 percent of dispersant; 0.2 to 1 percent of thickening agent; 0.1 to 0.3 percent of bactericide; 1-3% of pH neutralizer; 0.2 to 1 percent of adhesion promoter; 3 to 5 percent of cosolvent. The invention can obtain the water paint with multiple functions through a silicon-zirconium nano sol and resin water composite system, and the functions of the water paint comprise hardening, wear resistance, antibiosis, hydrophobicity, transparency, highlight and the like. The nano sol not only has high transparency, but also endows the coating with better performances in the aspects of hardness, wear resistance, hydrophobicity and the like. The invention also discloses a preparation method of the stainless steel composite functional coating.
Description
Technical Field
The invention belongs to the technical field of functional coatings, and particularly relates to a stainless steel composite functional coating which can be effectively applied to the fields of protection and functions of stainless steel materials. In addition, the invention also relates to a preparation method of the stainless steel composite functional coating.
Background
With the rapid development of modern industry, application scenes and environments of various materials become diversified, and various working indexes are stricter. The performance parameters of the material surface often cannot meet the requirements of an actual scene, surface functionalization treatment is needed, and the functional coating is an important direction in the future. The surface performance of the material can be greatly improved by coating the paint with multiple functions on the surface, so that the material meets the requirements of life and work. The method has a great pushing effect on social and economic development and technological progress.
Stainless steel is a common material and plays an important role in social and economic construction. In daily application, the service life and the application range are limited greatly due to the influence of environmental factors and the restriction of surface functions of the product. Therefore, the coating is protected and functionalized, not only is the utilization rate of steel resources and energy improved, but also the stainless steel material is favorably pushed to higher application fields, such as airplanes, high-speed rails, aerospace materials and the like. General stainless steel base material coatings are insufficient in gloss, hardness, abrasion resistance, water resistance, antibacterial property and the like. Therefore, a novel coating with powerful functions, simple preparation and environmental protection needs to be developed to meet the increasing demands of the market. Wherein, the nano sol such as silica sol, zirconium sol, aluminum sol and the like can form a compact network structure, and shows excellent performances in the aspects of hardness, wear resistance, hydrophobicity, antifouling property and the like. The nano sol, the functional components and the resin system are subjected to organic-inorganic hybrid compounding, and the obtained coating has the advantages of comprehensive and efficient performance and is a great development direction of the stainless steel coating.
Currently, nanosol-based coatings have achieved some research results. Chinese patent CN105462460 discloses a stainless steel water-based paint with stain resistance and fingerprint resistance, which has high hydrophobic and oleophobic effects and is insufficient in the multifunctional direction of glossiness, hardness and the like; chinese patent CN103540175 discloses a silica sol waterproof coating which has good waterproof and heat insulation effects, and the functional and application fields of the silica sol waterproof coating need to be developed; chinese patent CN106833319 discloses a water-based polycarbonate modified silica sol composite coating, which has high coating hardness, washing resistance and stain resistance, and needs to be improved in other properties such as adhesion, glossiness and the like.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art methods and techniques, it would be desirable to provide a stainless steel composite functional coating based on a nano sol of silicon and zirconium, which has excellent properties in terms of gloss, hydrophobicity, hardness, abrasion resistance, antibacterial properties, etc., according to embodiments of the present invention. In addition, the invention also hopes to provide a preparation method of the stainless steel composite functional coating.
Therefore, the invention adopts the following technical scheme:
a stainless steel composite functional coating based on silicon-zirconium nano sol comprises the following components in percentage by mass: 30-50% of acrylic resin; 5-20% of silicon-zirconium nano sol with the grain diameter of 15-30 nm; 10-20% of filler; 30-60% of deionized water; 0.2 to 1.5 percent of dispersant; 0.2 to 1 percent of thickening agent; 0.1 to 0.3 percent of bactericide; 1-3% of pH neutralizer; 0.2 to 1 percent of adhesion promoter; 3 to 5 percent of cosolvent.
The acrylic resin is waterborne modified epoxy acrylic resin; the filler is selected from nano titanium dioxide with the particle size of 5-30nm, mica powder, aluminum tripolyphosphate and zinc polyphosphate; the dispersant is ammonium polyacrylate; the thickening agent is selected from hydroxymethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose; the bactericide is silver-copper double-ion composite nano particles with the particle size of 3-20 nm; the pH neutralizer is selected from triethanolamine, N-methylethanolamine, butyldiethanolamine, and 2-amino-2-methyl-1-propanol; the adhesion promoter is selected from phosphate acrylate and epoxy phosphate; the co-solvent is selected from the group consisting of propylene glycol, isopropanol, butanol, and isobutanol.
In the technical scheme of the invention, the preparation method of the silicon-zirconium nano sol with the particle size of 15-30nm comprises the following steps:
(1) putting tetraethoxysilane into ethanol, putting zirconium acetate into water, wherein the molar ratio of tetraethoxysilane to zirconium acetate is 3:1, and the volume ratio of ethanol to water is 1: (0.2-1), stirring at constant speed for 0.5-1.5h respectively.
(2) Uniformly mixing the two solutions, and performing ultrasonic treatment for 10-30 min;
(3) adding polyvinyl alcohol accounting for 15-55% of the weight of the tetraethoxysilane into the mixed solution, then dripping acetic acid into the mixed solution to control the pH value to be 3-5, carrying out ultrasonic reaction for 0.5-2h at 50-60 ℃, and standing and aging for 24-48 h;
(4) and (3) carrying out suction filtration, repeatedly cleaning with ethanol for three times, and freeze-drying for 24-48h to obtain the silicon-zirconium nano sol with the particle size of 15-30 nm.
According to an embodiment, the invention also provides a preparation process of the stainless steel composite functional coating based on the silicon-zirconium nano sol, which comprises the following steps:
(1) weighing corresponding components according to the percentage, putting the cosolvent, the dispersant and the pH regulator into deionized water accounting for 70 percent of the total amount, and stirring at the stirring speed of 500-800r/min for 20-30 min;
(2) weighing corresponding components according to the percentage, adding the aqueous modified epoxy acrylic resin, the silicon-zirconium nano sol, the bactericide and the filler into the solution in the step (1), uniformly stirring at the speed of 1500-;
(3) the rotating speed is adjusted to be 500-800r/min, the thickening agent, the adhesion promoter and the residual deionized water are added, the mixture is stirred for 0.5 to 1h until the mixture is uniform, and the mixture is sieved by a 200-mesh screen to obtain the stainless steel composite functional coating based on the silicon-zirconium nano sol.
Compared with the prior art, the following examples and experimental examples prove that the stainless steel composite functional coating based on the silicon-zirconium nano sol prepared by the invention has multiple advantages: (1) the coating has excellent adhesive force, the hardness can reach 6H, and the wear resistance is outstanding; (2) the coating has good transparency, and the glossiness (60 degrees) reaches 82; (3) the coating has excellent hydrophobic property, and the contact angle reaches 118 degrees; (4) the coating has excellent antibacterial and antivirus performance, and the sterilization rate reaches 99.9 percent. The coating prepared by the invention is simple to prepare, simple and convenient in construction mode, green and environment-friendly in water-based coating, strong in function comprehensiveness and very wide in market application prospect.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. These examples are to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever. After reading the description of the invention, one skilled in the art can make various changes and modifications to the invention, and such equivalent changes and modifications also fall into the scope of the invention defined by the claims.
The starting materials used in the following examples of the present invention are all commercially available products unless otherwise specified.
Example 1
Firstly, preparing the silicon-zirconium nano sol.
The first step is as follows: adding 19g of tetraethoxysilane into 60ml of ethanol, adding 10g of zirconium acetate into 30ml of water, and respectively stirring at constant speed for 1 hour;
the second step is that: uniformly mixing the two solutions, and performing ultrasonic treatment for 10 min;
the third step: adding 5g of polyvinyl alcohol into the mixed solution, then dripping acetic acid into the mixed solution to control the pH value to be 5, carrying out ultrasonic reaction for 1h at 50 ℃, and standing and aging for 24 h;
the fourth step: and (4) carrying out suction filtration, repeatedly cleaning with ethanol for three times, and freeze-drying for 48 hours to obtain the silicon-zirconium nano sol with the average particle size of 20 nm.
The following ingredients were then weighed: 15g of silicon-zirconium nano sol, 35g of modified epoxy acrylic resin Paraloid A11, 6g of nano titanium dioxide with the particle size of 10nm, 2g of mica powder, 2g of zinc polyphosphate, 45g of deionized water, 0.5g of ammonium polyacrylate, 0.2g of hydroxyethyl cellulose, 0.1g of silver-copper composite nano particles, 2g of butyl diethanolamine, 0.3g of phosphate acrylate and 5g of isopropanol.
And finally, preparing the functional coating.
The first step is as follows: adding isopropanol, ammonium polyacrylate and butyldiethanolamine into 31.5g deionized water, and stirring at 500r/min for 20 min;
the second step is that: adding modified epoxy acrylic resin Paraloid A11, silicon-zirconium nano sol, silver-copper composite nano particles, nano titanium dioxide, mica powder and zinc polyphosphate into the solution in the first step, uniformly stirring at the speed of 1500r/min, and performing ball milling treatment for 1 h;
the third step: regulating the rotating speed to 500r/min, adding phosphate acrylate, hydroxyethyl cellulose and the rest 13.5g of deionized water, stirring for 1h until the mixture is uniform, and sieving the mixture by a 200-mesh sieve to obtain the stainless steel composite functional coating based on the silicon-zirconium nano sol.
Example 2
Firstly, preparing the silicon-zirconium nano sol.
The first step is as follows: adding 10g of ethyl orthosilicate into 50ml of ethanol, adding 5.2g of zirconium acetate into 20ml of water, and respectively stirring at constant speed for 0.5 h;
the second step is that: uniformly mixing the two solutions, and performing ultrasonic treatment for 10 min;
the third step: adding 3g of polyvinyl alcohol into the mixed solution, then dripping acetic acid into the mixed solution to control the pH value to be 4, carrying out ultrasonic reaction for 1h at 50 ℃, and standing and aging for 24 h;
the fourth step: and (4) carrying out suction filtration, repeatedly cleaning with ethanol for three times, and freeze-drying for 48 hours to obtain the silicon-zirconium nano sol with the average particle size of 16 nm.
The following ingredients were then weighed: 10g of silicon-zirconium nano sol, 30g of modified epoxy acrylic resin Paraloid A11, 8g of aluminum tripolyphosphate, 5g of zinc polyphosphate, 40g of deionized water, 0.3g of ammonium polyacrylate, 0.3g of hydroxyethyl cellulose, 0.1g of silver-copper composite nanoparticles, 1g N-methylethanolamine, 0.3g of epoxy phosphate and 5g of isobutanol.
And finally, preparing the functional coating.
The first step is as follows: putting isobutanol, ammonium polyacrylate and N-methylethanolamine into 28g of deionized water, and stirring at the stirring speed of 800r/min for 20 min;
the second step is that: adding modified epoxy acrylic resin Paraloid A11, silicon-zirconium nano sol, silver-copper composite nanoparticles, aluminum tripolyphosphate and zinc polyphosphate into the solution obtained in the first step, uniformly stirring at the speed of 1500r/min, and performing ball milling for 1 h;
the third step: adjusting the rotating speed to 800r/min, adding epoxy phosphate, carboxymethyl cellulose and the rest 12g of deionized water, stirring for 1h until the mixture is uniform, and sieving the mixture by a 200-mesh sieve to obtain the stainless steel composite functional coating based on the silicon-zirconium nano sol.
Example 3
Firstly, preparing the silicon-zirconium nano sol.
The first step is as follows: 20g of tetraethoxysilane is put into 80ml of ethanol, 10.5g of zirconium acetate is put into 40ml of water, and the materials are respectively stirred at a constant speed for 1 hour;
the second step is that: uniformly mixing the two solutions, and performing ultrasonic treatment for 30 min;
the third step: adding 5g of polyvinyl alcohol into the mixed solution, then dripping acetic acid into the mixed solution to control the pH value to be 4, carrying out ultrasonic reaction at 55 ℃ for 1.5h, and standing and aging for 36 h;
the fourth step: and (4) carrying out suction filtration, repeatedly cleaning with ethanol for three times, and freeze-drying for 48 hours to obtain the silicon-zirconium nano sol with the average particle size of 19 nm.
The following ingredients were then weighed: 20g of silicon-zirconium nano sol, 40g of modified epoxy acrylic resin Paraloid A11, 4g of nano titanium dioxide with the particle size of 15nm, 1g of mica powder, 5g of zinc polyphosphate, 50g of deionized water, 1g of ammonium polyacrylate, 0.2g of hydroxypropyl cellulose, 0.1g of silver-copper composite nano particles, 1g of triethanolamine, 0.3g of phosphate acrylate and 5g of propylene glycol.
And finally, preparing the functional coating.
The first step is as follows: putting propylene glycol, ammonium polyacrylate and triethanolamine into 35g of deionized water, and stirring at a stirring speed of 800r/min for 30 min;
the second step is that: adding modified epoxy acrylic resin Paraloid A11, silicon-zirconium nano sol, silver-copper composite nano particles, nano titanium dioxide, mica powder and zinc polyphosphate into the solution in the first step, uniformly stirring at the speed of 2000r/min, and performing ball milling treatment for 1.5 h;
the third step: adjusting the rotating speed to 800r/min, adding phosphate acrylate, hydroxypropyl cellulose and the rest 15g of deionized water, stirring for 1h until the mixture is uniform, and sieving the mixture by a 200-mesh sieve to obtain the stainless steel composite functional coating based on the silicon-zirconium nano sol.
Example 4
Firstly, preparing the silicon-zirconium nano sol.
The first step is as follows: adding 25g of tetraethoxysilane into 100ml of ethanol, adding 13.1g of zirconium acetate into 50ml of water, and respectively stirring at constant speed for 1.5 h;
the second step is that: uniformly mixing the two solutions, and performing ultrasonic treatment for 30 min;
the third step: adding 8g of polyvinyl alcohol into the mixed solution, then dripping acetic acid into the mixed solution to control the pH value to be 4, carrying out ultrasonic reaction for 2 hours at the temperature of 60 ℃, and standing and aging for 36 hours;
the fourth step: and (4) carrying out suction filtration, repeatedly cleaning with ethanol for three times, and freeze-drying for 48 hours to obtain the silicon-zirconium nano sol with the average particle size of 18 nm.
The following ingredients were then weighed: 20g of silicon-zirconium nano sol, 40g of modified epoxy acrylic resin Paraloid A11, 4g of mica powder, 7g of zinc polyphosphate, 56g of deionized water, 1.2g of ammonium polyacrylate, 0.2g of carboxymethyl cellulose, 0.1g of silver-copper composite nanoparticles, 1g of 2-amino-2-methyl-1-propanol, 0.7g of phosphate acrylate and 5g of isopropanol.
And finally, preparing the functional coating.
The first step is as follows: putting isopropanol, ammonium polyacrylate and 2-amino-2-methyl-1-propanol into 39.2g of deionized water, and stirring at a stirring speed of 800r/min for 30 min;
the second step is that: adding modified epoxy acrylic resin Paraloid A11, silicon-zirconium nano sol, silver-copper composite nano particles, mica powder and zinc polyphosphate into the solution in the first step, uniformly stirring at the speed of 2000r/min, and performing ball milling treatment for 2 hours;
the third step: adjusting the rotating speed to 800r/min, adding phosphate acrylate, carboxymethyl cellulose and the rest 16.8g of deionized water, stirring for 1h until the mixture is uniform, and sieving the mixture by a 200-mesh sieve to obtain the stainless steel composite functional coating based on the silicon-zirconium nano sol.
Example 5
Firstly, preparing the silicon-zirconium nano sol.
The first step is as follows: adding 15g of tetraethoxysilane into 80ml of ethanol, adding 7.9g of zirconium acetate into 40ml of water, and respectively stirring at constant speed for 1.5 h;
the second step is that: uniformly mixing the two solutions, and performing ultrasonic treatment for 30 min;
the third step: adding 8g of polyvinyl alcohol into the mixed solution, then dripping acetic acid into the mixed solution to control the pH value to be 3, carrying out ultrasonic reaction for 1h at 50 ℃, and standing and aging for 24 h;
the fourth step: and (4) carrying out suction filtration, repeatedly cleaning with ethanol for three times, and freeze-drying for 48 hours to obtain the silicon-zirconium nano sol with the average particle size of 20 nm.
The following ingredients were then weighed: 10g of silicon-zirconium nano sol, 35g of modified epoxy acrylic resin Paraloid A11, 4g of nano titanium dioxide with the particle size of 20nm, 5g of aluminum tripolyphosphate, 2g of zinc polyphosphate, 40g of deionized water, 0.6g of ammonium polyacrylate, 0.2g of hydroxymethyl cellulose, 0.1g of silver-copper composite nano particles, 1g of butyl diethanolamine, 0.5g of phosphate acrylate and 5g of butanol.
And finally, preparing the functional coating.
The first step is as follows: adding butanol, ammonium polyacrylate and butyldiethanolamine into 28g of deionized water, and stirring at a stirring speed of 800r/min for 30 min;
the second step: adding modified epoxy acrylic resin Paraloid A11, silicon-zirconium nano sol, silver-copper composite nano particles, nano titanium dioxide, aluminum tripolyphosphate and zinc polyphosphate into the solution in the first step, uniformly stirring at the speed of 2000r/min, and performing ball milling for 1 h;
the third step: adjusting the rotating speed to 800r/min, adding phosphate acrylate, hydroxymethyl cellulose and the rest 12g of deionized water, stirring for 0.5h until the mixture is uniform, and sieving the mixture by a 200-mesh sieve to obtain the stainless steel composite functional coating based on the silicon-zirconium nano sol.
Example 6
Firstly, preparing the silicon-zirconium nano sol.
The first step is as follows: adding 16g of tetraethoxysilane into 70ml of ethanol, adding 8.4g of zirconium acetate into 40ml of water, and respectively stirring at constant speed for 1 hour;
the second step: uniformly mixing the two solutions, and performing ultrasonic treatment for 20 min;
the third step: adding 3g of polyvinyl alcohol into the mixed solution, then dripping acetic acid into the mixed solution to control the pH value to be 5, carrying out ultrasonic reaction for 1h at the temperature of 55 ℃, and standing and aging for 24 h;
the fourth step: and (4) carrying out suction filtration, repeatedly cleaning with ethanol for three times, and freeze-drying for 48 hours to obtain the silicon-zirconium nano sol with the average particle size of 28 nm.
The following ingredients were then weighed: 10g of silicon-zirconium nano sol, 30g of modified epoxy acrylic resin Paraloid A11, 2g of nano titanium dioxide with the particle size of 20nm, 2g of aluminum tripolyphosphate, 2g of zinc polyphosphate, 35g of deionized water, 0.4g of ammonium polyacrylate, 0.4g of hydroxyethyl cellulose, 0.1g of silver-copper composite nano particles, 1g N-methylethanolamine, 0.4g of epoxy phosphate and 5g of isobutanol.
And finally, preparing the functional coating.
The first step is as follows: putting isobutanol, ammonium polyacrylate and N-methylethanolamine into 25g of deionized water, and stirring at the stirring speed of 600r/min for 20 min;
the second step is that: adding modified epoxy acrylic resin Paraloid A11, silicon-zirconium nano sol, silver-copper composite nanoparticles, nano titanium dioxide, aluminum tripolyphosphate and zinc polyphosphate into the solution obtained in the first step, uniformly stirring at the speed of 1500r/min, and performing ball milling treatment for 1 h;
the third step: adjusting the rotating speed to 800r/min, adding epoxy phosphate, hydroxyethyl cellulose and the rest 10g of deionized water, stirring for 0.5h until the mixture is uniform, and sieving by a 200-mesh sieve to obtain the stainless steel composite functional coating based on the silicon-zirconium nano sol.
Test examples
The coating in each example is coated on the surface of the treated stainless steel, and is baked at 80 ℃ for 120min to prepare a coating sample.
The films were tested for gloss, hydrophobicity, adhesion, pencil hardness, abrasion resistance, and antimicrobial effect. The glossiness (60 ℃) is tested by a glossiness meter, the hydrophobicity is tested by a full-automatic contact angle measuring instrument, the adhesive force is tested by a check method, the pencil hardness is tested according to GB/T6739-2006 related standards, the wear resistance is tested according to GB/T1768-2006 related standards, and the antibacterial and antivirus effects are obtained according to SGS related tests.
As can be seen from Table 1, the coating has high adhesion (0 grade), high hardness and wear resistance, and a certain high light effect; the hydrophobic angle is up to 118 degrees, and good hydrophobicity is shown; and, also has excellent bactericidal and antiviral properties.
In conclusion, the coating has better performances in the aspects of adhesion, hardness, wear resistance, hydrophobicity, antibiosis, antivirus and the like, and has high application value in the field of related functional requirements.
TABLE 1 coating Performance test of the examples
Claims (3)
1. The stainless steel composite functional coating is characterized by comprising the following components in percentage by mass:
30-50% of waterborne modified epoxy acrylic resin;
5-20% of silicon-zirconium nano sol with the grain diameter of 15-30 nm;
10-20% of filler;
30-60% of deionized water;
0.2 to 1.5 percent of dispersant;
0.2 to 1 percent of thickening agent;
0.1 to 0.3 percent of bactericide;
1-3% of pH neutralizer;
0.2 to 1 percent of adhesion promoter;
3-5% of cosolvent;
the filler is selected from nano titanium dioxide with the particle size of 5-30nm, mica powder, aluminum tripolyphosphate and zinc polyphosphate;
the dispersant is ammonium polyacrylate;
the thickener is selected from hydroxymethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose;
the bactericide is silver-copper double-ion composite nanoparticles with the particle size of 3-20 nm;
the pH neutralizer is selected from triethanolamine, N-methylethanolamine, butyldiethanolamine, and 2-amino-2-methyl-1-propanol;
the adhesion promoter is selected from phosphate acrylate and epoxy phosphate;
the co-solvent is selected from the group consisting of propylene glycol, isopropanol, butanol, and isobutanol.
2. The stainless steel composite functional coating of claim 1, wherein the preparation method of the silicon zirconium nano sol comprises the following steps:
(1) putting tetraethoxysilane into ethanol, putting zirconium acetate into water, wherein the molar ratio of tetraethoxysilane to zirconium acetate is 3:1, and the volume ratio of ethanol to water is 1: (0.2-1), stirring at constant speed for 0.5-1.5h respectively.
(2) Uniformly mixing the two solutions, and performing ultrasonic treatment for 10-30 min;
(3) adding polyvinyl alcohol accounting for 15-55% of the weight of the tetraethoxysilane into the mixed solution, then dripping acetic acid into the mixed solution to control the pH value to be 3-5, carrying out ultrasonic reaction for 0.5-2h at 50-60 ℃, and standing and aging for 24-48 h;
(4) and (3) carrying out suction filtration, repeatedly cleaning with ethanol for three times, and freeze-drying for 24-48h to obtain the silicon-zirconium nano sol with the particle size of 15-30 nm.
3. The preparation method of the stainless steel composite functional coating is characterized by comprising the following steps:
(1) weighing corresponding components according to the percentage, putting the cosolvent, the dispersant and the pH regulator into deionized water accounting for 70 percent of the total amount, and stirring at the stirring speed of 500-800r/min for 20-30 min;
(2) weighing corresponding components according to the percentage, adding the aqueous modified epoxy acrylic resin, the silicon-zirconium nano sol, the bactericide and the filler into the solution in the step (1), uniformly stirring at the speed of 1500-;
(3) the rotating speed is adjusted to be 500-800r/min, the thickening agent, the adhesion promoter and the residual deionized water are added, the mixture is stirred for 0.5 to 1 hour until the mixture is uniform, and the mixture is sieved by a 200-mesh screen to prepare the stainless steel composite functional coating based on the silicon-zirconium nano sol.
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