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CN-122011875-A - Water-based porcelain-gathering protective coating material and preparation method thereof

CN122011875ACN 122011875 ACN122011875 ACN 122011875ACN-122011875-A

Abstract

The invention discloses a water-based porcelain protective coating material and a preparation method thereof, which belong to the technical field of coating materials, wherein the water-based porcelain protective coating material can be coated on the surface of kitchen utensils and then solidified at low temperature to form a compact ceramic film layer, has super-hydrophobicity and photocatalysis self-cleaning capability, and is crosslinked with water-based titanium dioxide sol and modified nitrogen-doped silica sol together by taking polyacrylic acid as an organic flexible chain segment to form a three-dimensional crosslinking interpenetrating network, wherein the water-based titanium dioxide sol contains titanium dioxide and can endow the coating with photocatalysis self-cleaning performance and antibacterial property, the modified nitrogen-doped silica sol is mixed with graphite micro powder by taking urea as a nitrogen source, urea molecules can penetrate into pores and interlayers of the graphite micro powder, the problem that nitrogen element only stays on the surface in the traditional doping is solved, and the uniform doping of nitrogen element and tridecafluorooctyl triethoxysilane grafting can solve the problems that original graphite is strong in hydrophobicity and difficult to disperse in the water-based system.

Inventors

  • PU ZHIRUI
  • YAN XIN

Assignees

  • 深圳市深赛尔股份有限公司

Dates

Publication Date
20260512
Application Date
20260303

Claims (10)

  1. 1. The preparation method of the water-based porcelain protective coating material is characterized by comprising the following steps of: S1, performing acid-base neutralization reaction on titanyl sulfate and ammonia water to generate a metatitanic acid precipitate, and performing oxydol oxidation and ultraviolet irradiation to disperse the metatitanic acid precipitate to form aqueous titanium dioxide sol; s2, doping urea and graphitized anthracite micropowder, introducing liquid carbon dioxide into a high-pressure reaction kettle, and heating to obtain a nitrogen-doped graphite micropowder solution; S3, forming silica sol by using tetraethoxysilane under the catalysis of dilute hydrochloric acid, mixing the silica sol with the nitrogen-doped graphite micro powder solution, and performing aging treatment to obtain nitrogen-doped silica sol; s4, hydrolyzing and condensing hydroxyl of the nitrogen-doped silica sol and tridecafluorooctyl triethoxysilane in an ethanol solution to obtain modified nitrogen-doped silica sol; s5, carrying out free radical polymerization on the aqueous titanium dioxide sol, the modified nitrogen doped silica sol and the acrylic acid solution to obtain the aqueous porcelain protective coating material.
  2. 2. The method for preparing the aqueous porcelain protective coating material according to claim 1, wherein the mass ratio of the aqueous titanium dioxide sol to the modified nitrogen-doped silica sol is 2:1.
  3. 3. The method for preparing the aqueous porcelain protective coating material according to claim 1, wherein the specific preparation steps of the aqueous titanium dioxide sol are as follows: Adding 0.1-0.2mol/L titanyl sulfate aqueous solution and 50-60% ammonia water solution into a reaction kettle according to the volume ratio of 50-60:270-280, stirring for 20-40min at 20-25 ℃ and 500-600r/min, filtering, washing a filter cake with deionized water and absolute ethyl alcohol for 2-4 times until neutral, vacuum drying for 1-2h at 60-70 ℃ to obtain a metatitanic acid precipitate, adding the metatitanic acid precipitate and 20-30% hydrogen peroxide into the reaction kettle, stirring for 20-40min at 20-25 ℃ and 500-600r/min, then adding deionized water and 1-2% isopropanol, irradiating under an ultraviolet lamp with a center wavelength of 254nm, and continuing stirring for 4-5h to obtain an aqueous titanium dioxide sol; The dosage ratio of the metatitanic acid precipitate to the hydrogen peroxide to the deionized water to the isopropanol is 20-30g to 80-90mL to 50-60mL to 15-20mL.
  4. 4. The preparation method of the water-based porcelain protective coating material according to claim 1, which is characterized in that the specific preparation steps of the nitrogen-doped graphite micro powder solution are as follows: adding graphitized anthracite micropowder with the average particle size of 6-8 mu m, dispersant polyethylene glycol and urea solution with the mass fraction of 3-4% into a high-pressure reaction kettle, stirring for 20-40min at the temperature of 30-35 ℃ and the speed of 500-600r/min, pumping liquid carbon dioxide into the reaction kettle, enabling the pressure of carbon dioxide in the kettle to reach 35-40MPa, maintaining for 1-2h, discharging carbon dioxide, repeating the operation for 4-5 times, heating to 200-250 ℃, continuing to stir and react for 2-3h, and naturally cooling to room temperature to obtain the nitrogen-doped graphite micropowder solution.
  5. 5. The method for preparing the aqueous porcelain bushing protective coating material according to claim 4, wherein the dosage ratio of graphitized anthracite micro powder, polyethylene glycol, urea solution and liquid carbon dioxide is 50-60g:1-2g:20-25mL:12-14mL.
  6. 6. The preparation method of the water-based porcelain protective coating material according to claim 1, wherein the specific preparation steps of the nitrogen-doped silica sol are as follows: Adding 1.8-2.0g/L of ethyl orthosilicate solution, deionized water and 0.2-0.4mol/L of dilute hydrochloric acid into a reaction kettle, stirring for 20-40min at 20-25 ℃ and 500-600r/min, adding nitrogen-doped graphite micro powder solution, and continuing stirring and ageing for 1-2h to obtain nitrogen-doped silica sol.
  7. 7. The method for preparing the aqueous porcelain protective coating material according to claim 6, wherein the dosage ratio of the ethyl orthosilicate solution, the deionized water, the dilute hydrochloric acid and the nitrogen-doped graphite micro powder solution is 80-90mL:120-140mL:5-8mL:70-80mL.
  8. 8. The preparation method of the water-based porcelain protective coating material according to claim 1, wherein the specific preparation steps of the modified nitrogen-doped silica sol are as follows: Adding nitrogen-doped silica sol, tridecafluorooctyl triethoxysilane, absolute ethyl alcohol and deionized water into a reaction kettle, regulating the pH value to 3-4 by using a hydrochloric acid solution, stirring for 24-26 hours at 20-25 ℃ and 500-600r/min, filtering, washing the precipitate with deionized water and absolute ethyl alcohol for 2-4 times, and vacuum-drying for 1 hour at 60-70 ℃ to obtain modified nitrogen-doped silica sol; the dosage ratio of the nitrogen doped silica sol to the tridecafluorooctyl triethoxysilane to the anhydrous ethanol to the deionized water is 100-120g, 75-80mL, 200-250mL and 700-800mL.
  9. 9. The preparation method of the water-based porcelain protective coating material according to claim 1, wherein the water-based porcelain protective coating material comprises the following specific preparation steps: Adding aqueous titanium dioxide sol, modified nitrogen-doped silica sol, acrylic acid solution with neutralization degree of 40-50% and deionized water into a reaction kettle, introducing nitrogen for protection, stirring and reacting for 1-2 hours at 70-80 ℃ and 500-600r/min, cooling to 50-60 ℃, adding ammonium persulfate serving as an initiator and methylolacrylamide serving as a cross-linking agent into the reaction kettle, continuously stirring for 1-2 hours, filtering, washing a filter cake with ionized water and absolute ethyl alcohol for 2-4 times respectively, and vacuum drying for 1-2 hours at 60-70 ℃ to obtain an aqueous porcelain protective coating material; The aqueous titanium dioxide sol, the modified nitrogen doped silica sol, the acrylic acid solution, the deionized water, the ammonium persulfate and the methylol acrylamide are in a dosage ratio of 70-80g:35-40g:100-120mL:2-3L:2-3g:1-2g, the acrylic acid solution with the neutralization degree of 50-60% adopts a sodium hydroxide solution with the mass fraction of 5-10% as a neutralizing agent, the pH value of a system target is controlled to be 6.0-7.5 in the neutralization process, and the electric conductivity is maintained to be 1000-2000 mu S/cm.
  10. 10. An aqueous porcelain-polymer protective coating material, characterized in that it is produced by the production method according to any one of claims 1 to 9.

Description

Water-based porcelain-gathering protective coating material and preparation method thereof Technical Field The invention belongs to the technical field of coating materials, and particularly relates to a water-based porcelain protective coating material and a preparation method thereof. Background In recent years, the super-hydrophilic functional surface has a good application prospect in various fields such as building bathroom, biomedical, antifouling materials, electronic machinery and the like by virtue of special surface wettability, so that the super-hydrophilic functional surface is widely focused and rapidly developed. However, in the field of kitchen appliances, the surface protection requirements are more special, namely, equipment such as a gas cooking bench, an oven, cookware, a range hood and the like are in a high-temperature environment for a long time, oil dirt and oil dirt are easily adhered to the surface and the inner wall due to high temperature influence, and are difficult to clean, the existing industry mainly performs surface protection on the kitchen appliances in a coating spraying mode, however, the existing related coating technology has obvious short plates, and cannot completely match the comprehensive requirements of high temperature resistance, oil dirt resistance, easy cleaning and corrosion resistance. In particular, the existing kitchen utensil coating technology mainly has three scheme defects that the silicate coating is adopted, a basic protective layer can be formed, but the coating is not compact in structure, a large number of holes are formed in the coating due to the fact that foaming is easy to occur after the coating is used at high temperature, oil stains and oil dirt are easy to remain in the holes and are difficult to clean thoroughly, and more importantly, when the cleaning agent is used for cleaning, base material metal can be corroded due to the fact that the holes of the coating are exposed, the coating is finally triggered to fall off, and serious corrosion resistance and durability problems exist. The second scheme is to prepare the coating by using phosphate, epoxy modified organosilicon resin powder and high-temperature-resistant curing agent powder, and the coating can meet the high-temperature corrosion-resistant requirement, solves the stability problem at high temperature, but does not have the core functions of easy cleaning and oil stain resistance, and still cannot solve the oil stain adhesion pain point of kitchen utensils. The third scheme adopts fluorine-containing polymer with double-end silane structure, belonging to the category of organic coating, which has certain wear resistance and easy cleaning performance, but has insufficient temperature resistance, is only suitable for normal temperature or medium and low temperature environment, and can not be adapted to the high temperature working scene of kitchen appliances such as gas stove, oven, etc., and the problems of softening coating and functional failure easily occur at high temperature. The Chinese patent with the publication number of CN118791894B discloses a nano ceramic coating, a nano ceramic coating and a preparation method and application thereof, wherein silica sol and polysiloxane are used as film forming agents, and the silica sol and the polysiloxane are condensed and crosslinked to form bonds, so that the overlarge tensile stress caused by shrinkage between sol particles and the surface of a substrate can be reduced, the formed coating is prevented from self-cracking, meanwhile, nano powder is used as a filler, molecular gaps after dehydration and polycondensation of the silica sol can be filled and pinned as a coating with a reinforced relatively formed network structure, thus the compactness of the coating is improved, the formed coating is ensured to have no microcrack, greasy dirt and oil dirt are prevented from remaining in the coating, good cleanability and durability are ensured, but the coating possibly becomes a photocatalytic active center under long-term strong ultraviolet irradiation, the breakage of polysiloxane molecular chains is accelerated, the surface of the coating is gradually roughened, hydrophobicity is reduced, and finally the cleanability is lost, and durability is compromised. Disclosure of Invention The invention aims to provide a water-based porcelain protective coating material and a preparation method thereof, wherein the surface of the coating has superhydrophobicity and photocatalysis self-cleaning capability, and can decompose organic pollutants under ultraviolet irradiation, so that the surface is kept clean. The aim of the invention can be achieved by the following technical scheme: the preparation method of the water-based porcelain protective coating material comprises the following steps: s1, performing acid-base neutralization reaction on titanyl sulfate and ammonia water to generate a metatitanic acid precipitate, and performing oxydol