Ceramic surface protectant and methods of making and using same

Abstract

The present application belongs to the technical field of ceramic surface treatment, and particularly relates to a ceramic surface protective agent and a preparation method and use method thereof. The ceramic surface protective agent comprises, in parts by weight, 79-92 parts of a condensate, 2-5 parts of an intermediate, 1-3 parts of an emulsifier, 3-8 parts of a zirconium sol, 0.5-2 parts of a nano filler, and 1-3 parts of a hardening agent. The condensate is solid paraffin, the intermediate is glycerol or 1,2-propanediol, the nano filler is a mixture of one or more of zirconium oxide, yttrium sesquioxide and chromium sesquioxide, and the hardening agent is polyethylene wax. The present application aims to develop a new type of ceramic protective agent and a preparation method and use method thereof, greatly improve the corrosion resistance of ceramic plates, and simultaneously have excellent antifouling performance.

Description

Technical Field

[0001] This invention belongs to the field of ceramic surface treatment technology, and specifically relates to ceramic surface protective agents and their preparation and application methods. Background Technology

[0002] Architectural ceramics typically consist of a body layer, a decorative pattern layer, and a transparent glaze layer. The transparent glaze layer is predominantly a glassy phase, a transparent glass containing some crystalline and gaseous phases. The main component of the glassy phase is aluminosilicate. The chemical composition of the glaze layer in architectural ceramics presents significant challenges to its chemical corrosion resistance, especially its resistance to strong acids and alkalis. However, chemical corrosion resistance is a key requirement for ceramics. For example, GB / T 3810.13-2016 details the test methods and grading standards for the chemical corrosion resistance of ceramics. The 2025 Ceramic Tile Consumer Product Grading Standard GB / T 45817-2025 clarifies the grading requirements for ceramics from 3A to 5A. Currently, with the technological upgrading of the ceramic industry, 5A-grade ceramics have become a new research and development target for the entire ceramic industry. Among these, the performance requirement for resistance to strong acids and alkalis must reach Grade A.

[0003] Silica and α-alumina in ceramics exhibit good acid resistance but poor alkali resistance, especially to strong alkalis. Adjusting the chemical composition of ceramics themselves cannot solve the bottleneck problem of strong alkali resistance. Therefore, forming a protective layer on the ceramic surface through surface treatment is an important method to address chemical corrosion resistance. Several ceramic surface treatment agents have been disclosed. Patent CN201710763540.9 discloses a high-hardness matte ceramic anti-fouling agent, which is made by modifying and grafting active MQ silicone resin onto the surface of nano-silica particles, primarily to improve the wear resistance and anti-fouling properties of matte tiles. Patent CN202310527596.X discloses an anti-fouling and anti-slip surface treatment agent for ceramic slabs, with paraffin wax, hydrogen-containing silicone oil, solvent-based silica, and flake alumina as main components, simultaneously achieving anti-fouling and anti-slip properties. Patent CN201510026840.X discloses a ceramic tile anti-fouling agent, with methyl hydrogen-containing silicone oil and silicone rubber as main components, improving the anti-fouling performance of ceramic slabs. Patent CN202010099429.6 discloses an emulsion-type ceramic antifouling agent, with methyl silicone oil, hydrogen-containing silicone oil, amino silicone oil, hydroxyl silicone oil, and emulsifier as the main components, utilizing the synergistic effect of the components to improve the antifouling performance of ceramic tiles. Patent CN202010987376.1 discloses a multifunctional antifouling agent, with fluorinated modified silicone oil, hydrogen-containing silicone oil, inorganic powder, beeswax, and coupling agent as the main components, to improve the antifouling performance of ceramic tiles.

[0004] Based on the above technologies, it is clear that most existing ceramic surface treatment agents use silicone oil, modified silicone oil, or silicone resin as organic components and inorganic nanoparticles as additives. Their main purpose is to improve anti-fouling, anti-slip, or wear-resistant properties. Furthermore, these known ceramic surface treatment agents cannot improve corrosion resistance. Summary of the Invention

[0005] The present invention aims to develop a novel ceramic protective agent system and its preparation and application methods, which significantly improves the corrosion resistance of ceramic plates and also has excellent anti-fouling properties.

[0006] In a first aspect, the present invention provides a ceramic surface protectant. The ceramic surface protectant comprises, by weight, 79-92 parts of an aggregate, 2-5 parts of an intermediate, 1-3 parts of an emulsifier, 3-8 parts of zirconium sol, 0.5-2 parts of a nanofiller, and 1-3 parts of a hardening agent; wherein the aggregate is solid paraffin wax, the intermediate is glycerol or 1,2-propylene glycol, the nanofiller is one or a mixture of zirconium oxide, yttrium trioxide, and chromium trioxide, and the hardening agent is polyethylene wax.

[0007] Preferably, the solid paraffin is a solid paraffin or microcrystalline paraffin with a melting point above 60°C.

[0008] Preferably, the particle size of the nanofiller is 20~200 nm.

[0009] Preferably, the nanofiller is chromium trioxide.

[0010] Preferably, the emulsifier is one or more of Span 60, Span 65, Span 80, and glyceryl monostearate.

[0011] Preferably, the zirconium sol has a mass concentration of 10% to 20%.

[0012] Preferably, the method for preparing zirconium sol includes: mixing zirconium salt, stabilizer, catalyst and reaction medium, then adding water and carrying out a hydrolysis reaction under stirring conditions; after the reaction is completed, adjusting the pH value of the reaction solution to 4-5, and aging it to obtain zirconium sol.

[0013] Preferably, the zirconium salt is zirconium oxychloride and / or zirconium oxynitrate; the stabilizer is yttrium nitrate; the catalyst is hydrogen peroxide; and the reaction medium is at least one of anhydrous ethanol, methanol, and isopropanol.

[0014] Preferably, the molar ratio of zirconium salt, stabilizer, catalyst and reaction medium is 1:(0.06~0.12):(1.2~1.8):(8~12).

[0015] Secondly, the present invention provides a method for preparing a ceramic surface protectant. The preparation method includes: heating the aggregate until it is completely melted, adding an emulsifier under stirring conditions to mix it evenly; then adding a mixture composed of an intermediate, zirconium sol and nanofiller, maintaining the temperature at 100~120℃, and stirring to mix evenly; subsequently adding a hardening agent, and stirring to mix to obtain a liquid ceramic surface protectant.

[0016] Thirdly, the present invention provides a method for using a surface protectant for ceramic plates. The method includes:

[0017] (1) Inject the liquid ceramic surface protectant into the mold, stir continuously and cool to room temperature to obtain a block-shaped solid ceramic surface protectant;

[0018] (2) Add the solid ceramic surface protectant in block form to the dispensing machine, set the dispensing temperature to 100~120℃, and after heating, the ceramic surface protectant is applied to the ceramic surface to be treated in liquid form.

[0019] (3) The grinding head device presses the liquid ceramic surface protectant into the pore structure of the ceramic surface and forms a uniform, continuous and dense protective film layer on the ceramic surface.

[0020] Preferably, the amount of the ceramic surface protectant used is 20~50 g / m³. 2 .

[0021] The present invention has the following beneficial effects: it develops a novel ceramic plate protective agent system that is compatible with ceramic surface treatment processes, which can significantly improve the corrosion resistance of ceramics, especially the resistance to strong alkali corrosion; the ceramic plate protective agent system is firmly bonded to the substrate in the form of chemical bonds, thus having strong adhesion to the ceramic substrate; at the same time, the ceramic plate protective agent also has excellent anti-fouling properties. Detailed Implementation

[0022] The present invention is further illustrated by the following embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the present invention. The following exemplary methods illustrate the preparation and application of ceramic surface protectants.

[0023] Zirconium salt, stabilizer, catalyst and reaction medium are mixed, then water is added, and after stirring and hydrolysis, the pH value is adjusted to 4-5, and then aged to obtain zirconium sol.

[0024] Zirconium sol is a semi-transparent liquid in which nano-zirconia particles are dispersed in a medium. It possesses advantages such as high refractive index, high hardness, high wear resistance, excellent film-forming properties, and excellent corrosion resistance. The hydroxyl structure on the surface of zirconium sol also exhibits high reactivity. At a certain temperature, zirconium sol can react with the hydroxyl groups on the ceramic surface to form stable Si-O-Zr bonds, resulting in a continuous, uniform, dense, and highly transparent film. Based on these characteristics, this invention selects zirconium sol as a binder for the ceramic substrate.

[0025] The zirconium salt is at least one of zirconium oxychloride and zirconium oxynitrate. The stabilizer is preferably yttrium nitrate. The catalyst is preferably a hydrogen peroxide solution (30% by mass). The reaction medium is at least one of anhydrous ethanol, methanol, or isopropanol. In an optional embodiment, the molar ratio of zirconium salt, stabilizer, catalyst, reaction medium, and water is 1:(0.06~0.12):(1.2~1.8):(8~12):(21~23).

[0026] In an optional implementation, the hydrolysis temperature is 50~65℃. If the hydrolysis temperature is too low, hydrolysis cannot proceed; if the hydrolysis temperature is too high, the zirconium sol will gel.

[0027] In an optional implementation, the hydrolysis time is 1 to 3 hours. If the hydrolysis time is too short, the hydrolysis will be incomplete.

[0028] An appropriate amount of pH adjuster is added to adjust the pH of the hydrolysis reaction solution. The pH adjuster can be 1.5 mol / L ammonia solution. Below pH 4, the colloid is not fully formed. Above pH 5, a white precipitate appears, and the colloid is destroyed.

[0029] In an optional implementation, the aging time is 24-36 hours. The aging time affects the particle size.

[0030] The preferred particle size of the zirconium sol is 10–30 nm. Zirconium sol with this particle size exhibits the best performance in repairing porosity and microstructure on ceramic surfaces.

[0031] The aggregate was completely melted, and an emulsifier was added under stirring. Then, a mixture consisting of an intermediate, zirconium sol, and nanofillers was added. The temperature was maintained at 100–120°C, a hardening agent was added, and the mixture was stirred to obtain a liquid ceramic surface protectant. The aim was to prepare a protectant with molten paraffin as the continuous phase, tiny zirconium sol droplets as the dispersed phase, and inorganic nanoparticles as fillers.

[0032] The agglomerate is solid paraffin wax (including solid paraffin wax / microcrystalline wax), especially solid paraffin wax or microcrystalline wax with a melting point above 60°C (e.g., 60~95°C). Solid paraffin wax is a hydrocarbon substance, translucent at room temperature, melts upon heating, and solidifies upon cooling. Solid paraffin wax is chemically stable, possesses good lubrication properties, film-forming properties, excellent waterproof and moisture-proof properties, and exhibits excellent resistance to strong acids (concentrated sulfuric acid, concentrated hydrochloric acid, concentrated phosphoric acid, and hydrofluoric acid, etc.) and strong alkalis (concentrated sodium hydroxide, concentrated potassium hydroxide, etc.). Therefore, solid paraffin wax is selected as the agglomerate in this invention. Solid paraffin wax can be heated to 95~100°C to ensure the agglomerate melts.

[0033] The intermediate is glycerol or 1,2-propylene glycol. Its main function is to protect the hydroxyl groups of the zirconium sol. The intermediate also exhibits excellent hygroscopic properties, effectively preventing self-gelling of the zirconium sol during heating.

[0034] The main function of the emulsifier is to encapsulate the zirconium sol droplets, ensuring their stable dispersion within the paraffin phase. The emulsifier is preferably one or a mixture of Span 60, Span 65, Span 80, and glyceryl monostearate.

[0035] The nanofiller is preferably at least one of zirconium oxide, yttrium oxide, and chromium oxide, with a particle size of 20-200 nm, especially chromium oxide. The nanofiller is preferably corrosion-resistant nano-metal oxide particles with excellent resistance to strong acids and alkalis. Its main function is to enhance the hardness, strength, wear resistance, and scratch resistance of the film after formation, as well as to adjust the gloss of the film. Furthermore, the nanoparticles and paraffin wax can form a superhydrophobic, self-cleaning surface, improving the film's resistance to fouling.

[0036] The hardening agent is polyethylene wax. The hardening agent forms a strong network structure in the paraffin wax, which greatly improves the hardness and scratch resistance of the paraffin wax. After adding the hardening agent, the mixture should be stirred rapidly for 5-10 minutes. Rapid stirring at a temperature of 100-120°C is to allow free water and the reaction medium to evaporate.

[0037] Liquid ceramic surface protectant is injected into a mold, continuously stirred, and cooled to room temperature to obtain a block-shaped solid ceramic surface protectant. Preparing a solid ceramic surface protectant with a fixed shape facilitates matching the feed hopper of a dispensing machine.

[0038] Experiments have shown that conventional film-forming agents such as acrylic acid and its modified emulsions, polyurethane and its modified emulsions, polydimethylsiloxane and its modified substances (including fluorinated modification), polymethylhydrosiloxane, polyalphaolefin (PAO), and silicone resins cannot replace the solid paraffin film-forming agent of this invention, and will show obvious corrosion marks in strong alkali resistance tests.

[0039] Experiments have shown that nano-silica, nano-alumina, nano-titanium dioxide, nano-cerium oxide, nano-iron oxide, nano-copper oxide, and other metal oxide nanoparticles cannot replace the chromium trioxide nanofiller of this invention, and will be severely corroded in acid and alkali resistance tests.

[0040] In the preparation method of ceramic surface protectants, the agglomerates are first melted, then an emulsifier is added, followed by a mixture of intermediates, zirconium sol, and nanofillers, and finally a hardening agent is added. Solid paraffin agglomerates are the most important component and need to be melted by heating before the emulsifier is added. The emulsifier is an oleophilic emulsifier and needs to be miscible with the paraffin first. The intermediates, zirconium sol, and nanofillers cannot be added first because the paraffin requires a period of heating to melt, and the solvent in the zirconium sol evaporates quickly, potentially resulting in the zirconium sol gelling before the paraffin is completely melted.

[0041] The following describes the application method of the ceramic surface protectant. The method involves molding the liquid ceramic surface protectant into a solid state, and then pressing it onto the ceramic surface using a grinding head. Alternatively, the liquid protectant can be directly applied to the ceramic slab surface. However, in actual production, continuous heating equipment and pipelines are required; otherwise, the liquid protectant will cool and solidify, clogging the pipelines. The following will provide specific examples illustrating the application method of the ceramic surface protectant.

[0042] Liquid ceramic surface protectant is injected into a block mold, stirred continuously, and cooled to room temperature to obtain a block-shaped solid ceramic plate surface protectant.

[0043] In the ceramic slab post-processing production line, the ceramic slabs to be processed pass through a high-speed rotating waxing device to coat their surface with a protective layer. The waxing device can consist of 15 to 25 sets of grinding heads, with 6 rotating grinding discs on each grinding head. The friction between the grinding discs and the ceramic slab surface generates localized high temperatures, which can reach over 100°C.

[0044] The solid ceramic surface protectant prepared according to this invention is added to a dispensing machine, and the dispensing temperature is set to 100~120℃. After being heated instantaneously by a heating device, the solid solid ceramic surface protectant is dripped onto the surface of the ceramic plate in a liquid state.

[0045] The ceramic plate to be processed first passes through 3 to 5 sets of heating grinding heads to rapidly raise the surface temperature of the ceramic plate. In the next 6 sets of dispensing grinding heads, a dispensing machine dropper is set in every two sets. Then it continues to pass through the remaining coating grinding heads. The grinding disc can press the liquid ceramic plate surface protectant into the pore structure of the ceramic plate surface and spin coat it evenly on the ceramic plate surface. After cooling, a uniform, continuous and dense protective film layer is formed.

[0046] This protective film layer exhibits excellent corrosion resistance, especially resistance to strong acids and alkalis. In this invention, the testing of the acid and alkali resistance is conducted in accordance with GB / T 3810.13-2016. Resistance to strong acids and alkalis includes resistance to weak acids and weak bases (low concentrations) and strong acids and strong bases (high concentrations). Specifically, the weak acid is hydrochloric acid with a volume fraction of 0.03% or citric acid with a volume fraction of 100 g / L; the weak base is a strong potassium oxide solution with a volume fraction of 30 g / L; the strong acid is hydrochloric acid with a volume fraction of 0.18% or lactic acid with a volume fraction of 0.05%; and the strong base includes a potassium hydroxide solution with a volume fraction of 100 g / L.

[0047] The present invention has the following positive effects:

[0048] 1. This invention develops a novel surface protectant for ceramic plates, using solid paraffin wax, zirconium sol, chromium trioxide nanoparticles, and a hardening agent as the main components. After film formation, this protectant exhibits excellent chemical corrosion resistance and stain resistance, while also possessing good self-cleaning and wear resistance, making it significant for the preparation of 5A-grade ceramic products.

[0049] 2. This invention employs a water-in-oil system, in which zirconium sol is coated in a paraffin phase. The intermediate effect is used to protect the hydroxyl groups of the zirconium sol. During use, the zirconium hydroxyl groups can react with the hydroxyl groups on the surface of the ceramic plate to form stable Si-O-Zr bonds, which greatly increases the adhesion between the ceramic protective film and the substrate.

[0050] 3. The ceramic surface protectant developed in this invention is in solid form, but melts into a liquid state when used, which facilitates storage and transportation, and allows for accurate control of the amount used during use.

[0051] 4. The ceramic surface protectant developed in this invention can form a continuous, uniform, and dense protective film on the surface of a ceramic slab. This film has high transparency, and the surface gloss can be adjusted, making it suitable for both glossy and matte ceramic slabs.

[0052] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are all within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below. Unless otherwise specified in the present invention, parts refer to parts by weight.

[0053] Example 1

[0054] Weigh out 322.3 g of zirconium oxychloride, 33 g of yttrium nitrate, 136 g of hydrogen peroxide solution (30% concentration), and 368 g of anhydrous ethanol in a 1:0.06:1.2:8 molar ratio, and place them in an Erlenmeyer flask. Then add 378 g of deionized water and hydrolyze the mixture at 50°C in a water bath for 1 hour with stirring. Adjust the pH to 4 by adding ammonia dropwise. Stop stirring and allow to age for 24 hours to obtain zirconium sol. Next, take 92 parts of solid paraffin wax with a melting point of 60°C and place it in another clean Erlenmeyer flask. Heat to 95°C until the paraffin wax is completely melted. Then, add 1 part of emulsifier (Span 80) with stirring. After mixing thoroughly, add a mixture of 2 parts glycerol, 3 parts zirconium sol, and 0.5 parts of 20 nm nano-chromium trioxide. Maintain the temperature at 100°C, add 1 part of polyethylene wax, and stir rapidly for 5 minutes to obtain a liquid ceramic surface protectant. A ceramic surface protective agent is injected into a square mold, stirred, and cooled to room temperature to obtain a square block of solid ceramic surface protective agent. Polished tiles are then processed through a post-processing production line consisting of 15 grinding heads. The first three sets are heating grinding heads, the next six sets are dispensing grinding heads, and every two sets of dispensing grinding heads have a dispensing nozzle installed at the front end. The remaining grinding heads are coating grinding heads used to evenly coat the protective agent. The dispensing machine is loaded with the solid ceramic surface protective agent prepared according to this invention. The amount of solid ceramic surface protective agent used is 35 g / m³. 2 The ceramic plates that have passed through the post-processing production line are marked as ceramic plate 1#.

[0055] Example 2

[0056] Weigh out 322.3 g of zirconium oxychloride, 66 g of yttrium nitrate, 204 g of hydrogen peroxide (30% by mass), and 552 g of anhydrous ethanol in a 1:0.12:1.8:12 molar ratio, and place them in an Erlenmeyer flask. Then add 414 g of deionized water and hydrolyze the mixture at 65°C in a water bath for 3 hours with stirring. Adjust the pH to 5 by adding ammonia dropwise. Stop stirring and allow the mixture to age for 36 hours to obtain zirconium sol. Next, take 79 parts of solid paraffin wax with a melting point of 95°C and place it in another clean Erlenmeyer flask. Heat to 100°C until the paraffin wax is completely melted. Then, add 3 parts of emulsifier (Span 60) with stirring. After mixing thoroughly, add a mixture of 5 parts of 1,2-propylene glycol, 8 parts of zirconium sol, and 2 parts of 20 nm nano-chromium trioxide. Maintain the temperature at 120°C, add 3 parts of polyethylene wax, and stir rapidly for 10 minutes to obtain a liquid ceramic surface protectant. Liquid ceramic surface protectant was injected into a square mold, stirred, and cooled to room temperature to obtain a square block of solid ceramic surface protectant. Polished tiles were then processed through a post-processing production line consisting of 25 grinding heads. The first three sets were heating grinding heads, the next six sets were dispensing grinding heads, with dispensing nozzles installed at the front of every two sets of dispensing grinding heads. The remaining grinding heads were coating grinding heads used to evenly coat the protectant. The dispensing machine contained the solid ceramic surface protectant prepared according to this invention. The dosage of the solid ceramic surface protectant was 35 g / m³. 2 The ceramic plates that have passed through the post-processing production line are marked as ceramic plate #2.

[0057] Example 3

[0058] Weigh out 322.3 g of zirconium oxychloride, 66 g of yttrium nitrate, 204 g of hydrogen peroxide (30% by mass), and 552 g of anhydrous ethanol in a 1:0.12:1.8:12 molar ratio, place them in an Erlenmeyer flask, and then add 400 g of deionized water. After stirring and hydrolyzing for 2 hours in a 60°C water bath, adjust the pH to 5 by adding ammonia dropwise. Stop stirring and allow to age for 30 hours to obtain zirconium sol. Then, take 85 parts of solid paraffin wax with a melting point of 70°C and place it in another clean Erlenmeyer flask. Heat to 100°C until the paraffin wax is completely melted. Add 2 parts of emulsifier (Span 80) while stirring, and mix thoroughly. Then, add a mixture of 4 parts of 1,2-propylene glycol, 5 parts of zirconium sol, and 2 parts of 100 nm nano-chromium trioxide. Maintain the temperature at 120°C, add 2 parts of polyethylene wax, and stir rapidly for 8 minutes to obtain a liquid ceramic surface protectant. Liquid ceramic surface protectant was injected into a square mold, stirred, and cooled to room temperature to obtain a square block of solid ceramic surface protectant. Polished tiles were then processed through a post-processing production line consisting of 20 grinding heads. The first three sets were heating grinding heads, the next six sets were dispensing grinding heads, with dispensing nozzles installed at the front of every two sets of dispensing grinding heads. The remaining grinding heads were coating grinding heads used to evenly coat the protectant. The dispensing machine contained the solid ceramic surface protectant prepared according to this invention. The amount of solid ceramic surface protectant used was 35 g / m³. 2 The ceramic plates that have passed through the post-processing production line are marked as ceramic plate #3.

[0059] Comparative Example 1

[0060] Weigh out 322.3 g of zirconium oxychloride, 66 g of yttrium nitrate, 204 g of hydrogen peroxide (30% by mass), and 552 g of anhydrous ethanol in a Erlenmeyer flask according to a molar ratio of 1:0.12:1.8:12. Add 400 g of deionized water and hydrolyze at 60°C in a water bath for 2 hours with stirring. Adjust the pH to 5 by adding ammonia dropwise. Stop stirring and allow to age for 30 hours to obtain zirconium sol. Then, take 85 parts of aqueous acrylic emulsion and add 2 parts of emulsifier (Span 80) to each mixture while stirring. After thorough mixing, add a mixture of 4 parts of 1,2-propylene glycol, 5 parts of zirconium sol, and 2 parts of 100 nm nano-chromium trioxide. Maintain the temperature at 120°C and add 2 parts of polyethylene wax, stirring rapidly for 8 minutes. Obtain a liquid ceramic surface protectant. The polished tiles were processed through a post-processing production line consisting of 20 grinding heads. The first three sets were heating grinding heads, the next six sets were dispensing grinding heads, with liquid droppers installed at the front of every two sets of dispensing grinding heads. The remaining grinding heads were coating grinding heads used to evenly apply the protective agent. The dispensing machine contained the solid ceramic surface protective agent prepared in this comparative proportion. The usage amount of the solid ceramic surface protective agent was 35 g / m². 2 After processing, ceramic plate #4 was obtained.

[0061] The aqueous acrylic emulsion was replaced with equal amounts of methyl silicone oil, hydrogen-containing silicone oil, fluorinated silicone oil (perfluorosilicone oil), silicone-acrylic emulsion, and polyurethane emulsion, respectively, and ceramic plates 5#, 6#, 7#, 8#, and 9# were obtained after corresponding treatment.

[0062] The gloss of the ceramic slabs was tested using a KOSAI WGG60-Y4 gloss meter with a test graduation of 0.1 GU.

[0063] The corrosion resistance of ceramic slabs was determined in accordance with GB / T 3810.13-2016 "Chemical Corrosion Resistance". The test items included resistance to household liquids, chemical reagents and swimming pool salts (ammonium chloride solution 100g / L, sodium hypochlorite solution 20mg / L), as well as resistance to low concentrations (3% hydrochloric acid solution, citric acid solution 100g / L and potassium hydroxide solution 30g / L) and high concentrations of acids and alkalis (18% hydrochloric acid solution, 5% lactic acid solution and potassium hydroxide solution 100g / L).

[0064] The stain resistance of ceramic slabs was tested in accordance with GB / T 3810.14-2016 "Test Methods for Ceramic Tiles Part 14: Stain Resistance".

[0065] The performance test results are shown in Tables 1 and 2.

[0066] Table 1 Chemical Corrosion Resistance Test

[0067]

[0068] Table 2 Stain resistance and surface gloss test

[0069]

[0070] As can be seen from Tables 1 and 2, the ceramic surface protectant of the present invention exhibits excellent resistance to contamination and chemical corrosion after film formation, with a contamination resistance level of 5 and chemical corrosion resistance (especially resistance to strong alkalis) reaching level A. In contrast, Comparative Example 1 showed corrosion marks in all cases during the corrosion resistance test. Furthermore, Table 2 also shows that the surface gloss of the ceramic surface protectants treated in each embodiment differs, which is due to the different nano-chromium trioxide content and particle size of the ceramic surface protectants in each embodiment.

[0071] The surface of the ceramic plate No. 3 prepared in Example 3 after the strong acid and strong alkali resistance test shows that there are no circular traces of acid and alkali corrosion on the surface.

[0072] The ceramic plate 5# (methyl silicone oil film-forming agent) prepared in Comparative Example 1 showed obvious circular corrosion marks on its surface after strong acid and strong alkali tests. Significant differences in gloss were observed at the strong alkali test sites, indicating that the alkali solution penetrated the methyl silicone oil protective film and corroded the ceramic glaze.

[0073] After strong acid and strong alkali tests, the ceramic plate 7# (perfluorosilicone oil film-forming agent) prepared in Comparative Example 1 showed obvious circular corrosion marks on the surface of the ceramic plate.

[0074] The ceramic plate 9# (polyurethane emulsion film-forming agent) prepared in Comparative Example 1 showed obvious circular corrosion marks on its surface after strong acid and strong alkali resistance tests. After rinsing with water after the test, water pooled at the strong alkali test sites, indicating that the surface alkali solution damaged the polyurethane emulsion protective film and corroded the ceramic glaze.

[0075] Comparative Example 2

[0076] The only difference from Example 1 is that the formulation of the ceramic surface protectant is different.

[0077] The composition and performance test results of the ceramic surface protectant of Comparative Example 2 are shown in Tables 3, 4 and 5, respectively.

[0078] Table 3

[0079]

[0080] Table 4

[0081]

[0082] Table 5

[0083]

[0084] As can be seen from Table 5:

[0085] In Comparative Example 2-1, obvious circular corrosion marks appeared during the strong alkali corrosion resistance test. This is because the silica sol has extremely poor tolerance to alkali solutions.

[0086] Comparative Example 2-2 showed obvious circular corrosion marks during the strong alkali corrosion resistance test, which is due to the poor tolerance of nano-alumina to strong alkali solutions.

[0087] Comparative Examples 2-3 showed obvious circular corrosion marks during the strong alkali resistance test, which is due to the extremely poor tolerance of nano-silica to strong alkali solutions.

[0088] In Comparative Examples 2-4, agglomeration and stratification occurred in the prepared liquid ceramic plate surface protectant. This was due to insufficient emulsifier, which prevented the zirconium sol from being uniformly dispersed in the paraffin system. Ultimately, this resulted in insufficient adhesion between the film and the substrate, and poor film durability.

[0089] In Comparative Examples 2-5, over-emulsification and stratification occurred in the prepared liquid ceramic plate surface protectant. This was due to the excessive amount of emulsifier, which led to enhanced molecular interaction at the interface, resulting in distortion, agglomeration, or accumulation, ultimately causing the emulsifier to lose stability.

[0090] In the actual production process, the curing speed of the film layer on the surface of the ceramic plate after the protective agent treatment in Comparative Examples 2-6 was relatively slow, which affected the subsequent film application process. As a result, the film wax mixed with the incompletely cured protective agent, affecting the surface quality of the ceramic plate.

[0091] In Comparative Examples 2-7, zirconium sol gelled and powdered during the curing process of the liquid ceramic plate surface protectant. This was due to the low content of intermediates, which failed to effectively protect the hydroxyl groups of the zirconium sol during the evaporation of water, leading to hydroxyl dehydration condensation and consequently insufficient adhesion between the film and the substrate.

[0092] In Comparative Examples 2-8, during the curing process of the liquid ceramic plate surface protectant, the curing time was prolonged and the surface became slippery after curing. This was due to an excessive amount of intermediate.

[0093] In Comparative Examples 2-9, the low density of zirconium sol particles was observed during the preparation of liquid ceramic plate protective agents. This was due to the low zirconium sol content and insufficient zirconium hydroxyl number, which prevented effective bonding with the substrate during subsequent use, thus affecting the durability of the film layer.

[0094] In Comparative Examples 2-10, zirconium sol particle agglomeration occurred during the preparation of the liquid ceramic plate protective agent. This was due to excessively high zirconium sol content, leading to an increased number of zirconium hydroxyl groups and a higher probability of hydroxyl group binding. This affected the transparency of the film layer during subsequent film formation.

[0095] The range of addition amounts has been experimentally verified. The addition amounts of zirconium sol, intermediates, and emulsifiers are very sensitive to the system. Even slight adjustments can significantly alter the performance.

[0096] In Comparative Example 2-11, during actual production, the film layer on the surface of the ceramic plate treated with the protective agent could not be cured. The liquid wax film layer was easily contaminated and wiped off. In addition, the density and continuity of the liquid film layer were poor, which seriously affected the stain resistance and corrosion resistance.

[0097] Comparative Example 2-12 showed shallow but visible circular corrosion marks during the strong alkali resistance test. This is because the film structure contains a hydrogen-containing silicone oil component, which has poor resistance to strong alkalis. Furthermore, the film's gloss decreased significantly, and its transparency was reduced, affecting the decorative effect of the ceramic surface.

[0098] In Comparative Example 2-13, wrinkling of the film layer occurred in the test area during the strong alkali resistance test. This is because the film layer structure contains acrylic emulsion components, which react with the strong alkali.

[0099] In Comparative Example 2-14, during the preparation of the liquid ceramic plate protective agent, the zirconium sol particles exhibited dehydration, gelation, and pulverization. This was due to the volatilization of the propanol intermediate during heating, which failed to protect the hydroxyl groups of the zirconium sol, thus affecting the adhesion between the protective film and the substrate and leading to a decrease in antifouling performance. Furthermore, the pulverized zirconium sol formed zirconium oxide powder, which significantly impacted the gloss of the film.

[0100] In Comparative Examples 2-15, during the preparation of the liquid ceramic plate protective agent, some zirconium sol particles exhibited dehydration and gelation. This was due to insufficient moisture retention of the ethylene glycol intermediate during heating, which prevented it from fully protecting the hydroxyl groups of the zirconium sol, thus affecting the adhesion between the protective film and the substrate and resulting in poor antifouling performance. Furthermore, the small amount of pulverized zirconium sol forming zirconium oxide powder negatively impacted the film's gloss. Moreover, ethylene glycol is highly toxic, posing significant risks to human health and the environment.

Claims

1. A ceramic surface protectant, characterized in that, The ceramic surface protective agent is composed of the following raw materials: by weight, 79-92 parts of aggregate, 2-5 parts of intermediate, 1-3 parts of emulsifier, 3-8 parts of zirconium sol, 0.5-2 parts of nanofiller, and 1-3 parts of hardener; wherein, the aggregate is solid paraffin wax, the intermediate is glycerol or 1,2-propylene glycol, the nanofiller is chromium trioxide, and the hardener is polyethylene wax; the solid paraffin wax is a solid paraffin wax with a melting point above 60°C; the particle size of the nanofiller is 20-100 nm; the emulsifier is one or a mixture of Span 60, Span 65, Span 80, and glyceryl monostearate; and the particle size of the zirconium sol is 10-30 nm. nm; The preparation method of the ceramic surface protectant includes: heating the aggregate until it is completely melted, adding an emulsifier under stirring conditions to make it mix evenly; then adding a mixture composed of intermediate, zirconium sol and nanofiller, maintaining the temperature at 100~120℃, and stirring to mix evenly; subsequently adding a hardening agent, stirring and mixing to obtain a liquid ceramic surface protectant.

2. The ceramic surface protectant according to claim 1, characterized in that, The solid paraffin is microcrystalline paraffin.

3. The ceramic surface protectant according to claim 1, characterized in that, The zirconium sol has a mass concentration of 10% to 20%.

4. The ceramic surface protectant according to claim 1, characterized in that, The preparation method of zirconium sol includes: mixing zirconium salt, stabilizer, catalyst and reaction medium, then adding water and carrying out hydrolysis reaction under stirring conditions; after the reaction is completed, adjusting the pH value of the reaction solution to 4~5, and aging to obtain zirconium sol; the stabilizer is yttrium nitrate; the reaction medium is at least one of anhydrous ethanol, methanol and isopropanol; wherein, the molar ratio of zirconium salt, stabilizer, catalyst and reaction medium is 1:(0.06~0.12):(1.2~1.8):(8~12).

5. The ceramic surface protectant according to claim 4, characterized in that, The zirconium salt is zirconium oxychloride and / or zirconium oxynitrate; the catalyst is hydrogen peroxide.

6. The method for preparing the ceramic surface protectant according to any one of claims 1 to 5, characterized in that, The preparation method includes: heating the aggregate until it is completely melted, adding an emulsifier under stirring to make it mix evenly; then adding a mixture composed of an intermediate, zirconium sol and nanofiller, maintaining the temperature at 100~120℃, and stirring to mix evenly; subsequently adding a hardening agent, and stirring to mix to obtain a liquid ceramic surface protectant.

7. The method of using the ceramic surface protectant according to any one of claims 1 to 5, characterized in that, The method of use includes: (1) Inject the liquid ceramic surface protectant into the mold, stir continuously and cool to room temperature to obtain a block-shaped solid ceramic surface protectant; (2) Add the solid ceramic surface protectant in block form to the dispensing machine, set the dispensing temperature to 100~120℃, and after heating, the ceramic surface protectant is applied to the ceramic surface to be treated in liquid form. (3) The grinding head device presses the liquid ceramic surface protectant into the pore structure of the ceramic surface and forms a uniform, continuous and dense protective film layer on the ceramic surface.

Images