Antifouling tile and preparation process thereof

Abstract

The present invention relates to the technical field of ceramic tiles, and in particular to an anti-fouling ceramic tile and a preparation process thereof. The preparation process comprises the following preparation steps: polishing the ceramic tile surface; waxing the ceramic tile surface, and applying at least A wax to the ceramic tile surface during the waxing process; the A wax comprises the following raw materials, by weight: 15-20 parts of silica sol, 64-76 parts of solvent, 1-5 parts of a grinding aid with a boiling point ≥260°C, 3-10 parts of an anti-fouling aid, and 1-5 parts of a coupling agent. A wax, B wax, and C wax are applied to the ceramic tile surface in sequence, wherein A wax can fill the tiny, loose holes formed after polishing the ceramic tile surface, making the tile surface smoother; B wax penetrates into the gaps in A wax, blocking the smaller micropores on the ceramic tile surface, forming a dense, hard, and stronger organic film integrated with the ceramic tile; and C wax can form a long-lasting protective film on the ceramic tile substrate, making the ceramic tile have better anti-fouling, wear resistance, and weather resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic tiles, in particular to an anti-fouling ceramic tile and a preparation process thereof. Background Art

[0002] Ceramic tiles have been widely used in the field of decoration due to their advantages of low cost, easy maintenance and good decorative effect.

[0003] Currently, some ceramic tiles on the market, such as white tiles, have only undergone a single anti-fouling test. Microscopic examination of these products reveals large, dense pores on the tile surface, making them highly susceptible to stains. When subjected to multiple anti-fouling tests, subsequent tests often fail. Consequently, after a period of use, these tiles are prone to anti-fouling failure and even stain seepage, impacting user experience. Summary of the Invention

[0004] The main purpose of the present invention is to provide an anti-fouling tile and a preparation process thereof, aiming to improve the technical problem that existing anti-fouling tile products can only achieve short-term anti-fouling effect and have poor long-term anti-fouling effect.

[0005] To achieve the above object, the present invention proposes a preparation process for anti-fouling tiles, comprising the following preparation steps:

[0006] S1. Polish the tile surface;

[0007] S2. After waxing the tile surface, the antifouling tile is obtained;

[0008] During waxing treatment, at least A wax is applied to the surface of the tile; the A wax comprises the following raw materials by weight: 15-20 parts of silica sol, 64-76 parts of solvent, 1-5 parts of grinding aid with a boiling point ≥260°C, 3-10 parts of antifouling agent and 1-5 parts of coupling agent.

[0009] The fired ceramic tile products are polished, including rough polishing, medium polishing and fine polishing, to make the surface of the ceramic tile smoother. Then, the polished bricks are waxed with A wax raw material for super clean and bright waxing. Among them, the main raw material of A wax is silica sol beads with a size of about 50-80nm, which are used to improve the brightness of the ceramic tile and fill the tiny and loose holes formed after the ceramic tile surface is polished. Generally, the surface brightness of the ceramic tile after waxing can reach 90-110 degrees.

[0010] The grinding aid with a boiling point ≥260°C in this solution refers to a water-soluble agent with a boiling point of approximately 260-320°C, such as glycerin, propylene glycol, and polyethylene glycol. Its primary functions are lubrication, grinding aids, and wax burnout prevention. Since the abrasive used in waxing is relatively hard, considerable pressure is applied to the brick surface during rubbing, which results in high temperatures. Without a high-temperature-resistant additive, it will evaporate during the heating process, potentially causing wax burnout and even smoke from the brick surface, preventing proper waxing. Antifouling agents include penetrants and leveling agents, specifically polyether silicone oil or other water-soluble silicone oils, which offer certain antifouling properties. In actual production, coupling agents such as KH 550 can be used.

[0011] Preferably, during the waxing treatment, wax A and wax B are applied to the surface of the ceramic tile in sequence; the wax B comprises the following raw materials, in parts by weight: 3-15 parts of silicone oil containing hydroxyl and hydrogen groups, 5-10 parts of a crosslinking agent, 1-5 parts of silane containing ethoxy and amino groups (such as methylhydroethoxysilane), 1-5 parts of modified organic silicon nanospheres, 65-75 parts of a solvent and 1-3 parts of a wax B catalyst.

[0012] Wax B is also an anti-fouling wax and is applied directly on wax A (wax A does not form a film and has some nano-scale gaps). Anti-fouling wax B is a composite material composed of silicone oil, cross-linking agent, modified silicone nano-microspheres and other raw materials compounded in the above proportions. After being diluted with a solvent, under the action of wax B catalyst, silicone oil, silane, cross-linking agent and modified silicone nano-microspheres cross-link with each other and penetrate into the base surface of the tile to produce a condensation reaction, blocking the micropores on the surface of the tile, forming a dense, hard and stronger organic film integrated with the tile, making the anti-fouling structure more complete, thereby forming a protective coating on the tile surface without changing the original surface permeability and appearance, and achieving waterproof, hydrophobic and anti-fouling effects. The main raw material of B wax besides solvent is silicone oil, which specifically includes conventional silicone oil, high-viscosity silicone oil and small molecule silicone oil. Small molecule silicone oil can penetrate into the nano-gaps between A waxes, solidify A wax after filling, and increase the toughness and firmness of the super clean and bright layer formed after the application of B wax, and has a better anti-fouling effect; moreover, the silicon (Si) methyl (-CH3) content in B wax is relatively high, and the surface protective film has a better hydrophobic effect. After waxing, the tile surface is easier to clean, further improving its anti-fouling effect.

[0013] The cross-linking agent of this solution can be polymethylsiloxane, such as methyltriethoxysilane, etc.; the solvent of this solution can be ethanol, petroleum ether, etc.

[0014] Preferably, the silicone oil contains at least 10-35% high-viscosity silicone oil and 10-35% small-molecule silicone oil, with the remainder being low-viscosity silicone oil; the viscosity of the high-viscosity silicone oil is 350-550 cP, the viscosity of the low-viscosity silicone oil is 20-50 cP, and the molecular weight of the small-molecule silicone oil is 150-170.

[0015] The longer the chain segment of the silicone oil, the higher the viscosity. The viscosity range of the high-viscosity silicone oil in this solution is 350-550 cP, which can be specifically dimethylsiloxane. In addition, the silicone oil also includes small molecule silicone oil, whose molecular weight is generally around 150-170, and small molecule hydrogen-containing silicone oil such as methylhydroethoxysilane can be used; the remainder is low-viscosity silicone oil, which can be methylhydrogensiloxane, etc.

[0016] Preferably, the B wax catalyst is a metal salt. Examples of metal salts that can be used in this solution include platinum, organotin, or chloroplatinic acid. These heavy metal salts catalyze a condensation reaction with organosilicon or hydroxyl substrates, allowing the B wax raw material to bind and penetrate the ceramic surface to form a dense, hard organic film.

[0017] Preferably, the preparation steps of the modified organic silicon nanospheres include: S01. mixing dimethylsilane, a crosslinking agent and trimethylsilane, and stirring in a sealed manner for 6-12 hours to obtain a mixture; S02. adding B wax catalyst to the mixture, and then adding a solvent (such as petroleum ether, xylene, ethyl acetate, methyl acetate) to dilute it, heating it to 60-100°C and reacting it at a constant temperature for 12-24 hours to obtain the modified organic silicon nanospheres.

[0018] This solution introduces modified silicone nanospheres. The modified silicone nanospheres adopt the above-mentioned modification steps, and the size of the liquid state is about 0.1-1nm. The surface of the obtained modified silicone nanospheres contains methyl and hydroxyl groups, which can participate in the condensation reaction of silicone resin. At the same time, the nano-scale rigid particles are introduced into the anti-fouling wax B wax, which, on the one hand, helps to increase the hardness and toughness of the anti-fouling wax B wax, and on the other hand, it can also reduce the volume shrinkage of the anti-fouling wax. Even if it is left stationary for a long time, the anti-fouling material that penetrates into the pores will not decay.

[0019] The mass ratio of the dimethylsilane, the cross-linking agent and the trimethylsilane is (2-5): (1-4): (2-5), preferably 3.7:2.8:3.5.

[0020] Preferably, during the waxing treatment, A wax, B wax and C wax are applied to the surface of the tile in sequence; the C wax comprises the following raw materials, in parts by weight: 5-10 parts of methyl hydrogen siloxane, 3-8 parts of silane (methyl hydrogen ethoxysilane or hexadecyltriethoxysilane, etc.), 1-3 parts of C wax catalyst and 79-92 parts of solvent (such as anhydrous ethanol, etc.).

[0021] This solution also allows the application of Wax A, Wax B, and Wax C to the tile surface in sequence. Wax C, the tile antifouling wax, is a highly active organosilicon polymer composed of methylhydrogensiloxane and specialized long-methyl chain silanes such as methylhydrogenethoxysilane or hexadecyltriethoxysilane. Highly active amino and long methyl groups are grafted onto the silicon base. Under the action of the Wax C catalyst, Wax C reacts on the tile surface and penetrates the tile substrate, forming a transparent, dense protective layer. This layer remains waterproof (hydrophobic), antifouling, and easy-to-clean finish without altering the original tile's surface permeability or appearance.

[0022] The core working principles of anti-fouling wax C wax include: first, after the highly active functional groups penetrate and grow on the tile substrate through chemical reactions, their methyl groups form a long-lasting protective film; second, the hydroxyl groups form hydrophobic and oleophobic coatings through hydroxyl condensation reactions; third, by changing the microstructure of the tile surface, it better combines with C wax, making the tile surface have a higher hydrophobic angle, and the wear resistance and weather resistance of the tiles are also improved.

[0023] Preferably, the C wax catalyst is a super acid polymer. The super acid polymer catalyst used in this solution can be trifluoromethanesulfonic acid, which promotes the rapid reaction of the various raw materials of the anti-fouling wax C wax on the surface of the tile to form a protective layer on the surface of the tile.

[0024] Preferably, the ceramic tile surface is sequentially applied with 2 times of wax A, 1 time of wax B and 1 time of wax C. When waxing, one machine or multiple machines can be used, individually or in groups.

[0025] The present invention also provides an antifouling tile produced using any of the above-described processes for producing antifouling tiles. Because this antifouling tile utilizes all of the technical solutions of the above-described processes for producing antifouling tiles, it at least possesses all of the benefits provided by the above-described technical solutions, and no further details will be given here.

[0026] Compared with the prior art, the anti-fouling ceramic tile and its preparation process of the present invention have the following beneficial effects: first, wax A is applied to the surface of the ceramic tile to improve the brightness of the ceramic tile and fill the tiny, loose holes formed after the ceramic tile surface is polished, making the ceramic tile surface smoother; then, anti-fouling wax B is applied on wax A. Under the action of wax B catalyst, the silicone oil, silane, cross-linking agent and modified organic silicon nano-microspheres in wax B cross-link with each other and penetrate into the base surface of the ceramic tile to produce a condensation reaction, penetrate into the gaps of wax A to block the smaller micropores on the ceramic tile surface, and form a dense, hard and stronger organic film integrated with the ceramic tile, making the anti-fouling structure more complete, playing the role of waterproof, hydrophobic and anti-fouling effect; finally, apply C wax on the surface of the tile. Anti-fouling wax C wax is a highly active silicone polymer composed of small molecule silicone oil and special long methyl chain silane. Highly active amino functional groups and long methyl functional groups are grafted on the silicon base. After the highly active functional groups penetrate and grow on the tile substrate through chemical reactions, their methyl groups form a long-lasting protective film and form a hydrophobic and oleophobic coating through hydroxyl condensation reaction. At the same time, the microstructure of the tile surface is changed, which can better combine with C wax, so that the tile surface has a higher hydrophobic angle, further improving the anti-fouling effect. After one application of the above three anti-fouling waxes, the tiles have a long-term and effective anti-fouling effect, and their wear resistance and weather resistance are also improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0028] Figure 1 This is a microscopic picture of the ceramic tile in this solution that has passed the anti-fouling test;

[0029] Figure 2 This is a microscopic picture of the ceramic tile in this solution that shows "slightly absorbed dirt" after anti-fouling testing;

[0030] Figure 3 This is a microscopic picture of the ceramic tile in this solution that has “severely absorbed dirt” after the anti-fouling test.

[0031] The realization of the objectives, functional features and advantages of this application will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0032] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0033] In addition, the technical solutions between the various embodiments can be combined with each other, but they must be based on the fact that ordinary technicians in this field can implement them. When the combination of technical solutions is mutually contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0034] A preparation process for antifouling ceramic tiles comprises the following preparation steps:

[0035] S1. Polish the tile surface;

[0036] S2. After waxing the tile surface, the antifouling tile is obtained;

[0037] When waxing, apply A wax, B wax and C wax on the tile surface in sequence;

[0038] The A wax comprises the following raw materials in parts by weight: 15-20 parts of silica sol, 64-76 parts of solvent, 1-5 parts of grinding aid with a boiling point of ≥260°C, 3-10 parts of antifouling agent and 1-5 parts of coupling agent.

[0039] The B wax comprises the following raw materials, in parts by weight: 3-15 parts of silicone oil, 5-10 parts of a crosslinking agent, 1-5 parts of a silane, 1-5 parts of modified organic silicon nanospheres, 65-75 parts of a solvent, and 1-3 parts of a B wax catalyst; the silicone oil comprises at least 10-35% of a high-viscosity silicone oil and 10-35% of a small-molecule silicone oil, with the remainder being a low-viscosity silicone oil; the viscosity of the high-viscosity silicone oil is 350-550 cP, the viscosity of the low-viscosity silicone oil is 20-50 cP, and the molecular weight of the small-molecule silicone oil is 150-170; the B wax catalyst is a metal salt;

[0040] The preparation steps of the modified organic silicon nanoparticles include: S01. mixing dimethylsilane, a crosslinking agent and trimethylsilane (the mass ratio of the three is (2-5): (1-4): (2-5)), sealing and stirring for 6-12 hours to obtain a mixture; S02. adding B wax catalyst to the mixture, then adding solvent to dilute it, heating to 60-100°C and reacting at a constant temperature for 12 hours to 24 hours to obtain the modified organic silicon nanoparticles.

[0041] The C wax comprises the following raw materials in parts by weight: 5-10 parts of silicone oil, 3-8 parts of silane, 1-3 parts of C wax catalyst and 79-92 parts of solvent; the C catalyst is a super acid polymer.

[0042] The technical solutions of the present invention are further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0043] Blank group (polishing only, no waxing)

[0044] The same batch of marble tiles produced by Guangdong Jianyi Group Ceramics Co., Ltd. were subjected to the following polishing process. The specific arrangement of the polishing modules is as follows: rough polishing (15 groups of 600-mesh modules, 5 groups of 800-mesh modules) - medium polishing (6 groups of 600-mesh modules, 14 groups of 800-mesh modules) - fine polishing (4 groups of 1000-mesh modules, 4 groups of 1200-mesh modules, 4 groups of 1500-mesh modules, 4 groups of 2000-mesh modules, and 4 groups of 3000-mesh modules).

[0045] The following embodiments and comparative examples were polished and then waxed according to the above polishing process.

[0046] Example 1 (applying wax A in this solution)

[0047] The polished ceramic tile surface of the blank group was waxed: specifically, wax A was applied to the ceramic tile surface; wax A included the following raw materials, by weight: 18 parts of silica sol, 70 parts of solvent (deionized water), 2 parts of high boiling point additive (glycerol), 6 parts of antifouling additive (polyether silicone oil) and 4 parts of coupling agent (silane coupling agent).

[0048] Comparative Example 1

[0049] The polished ceramic tile surfaces of the blank group were waxed: specifically, conventional wax water similar to wax A produced in Foshan on the market was applied to the ceramic tile surfaces.

[0050] The waxed tiles of the blank group, Example 1 and Comparative Example 1 were subjected to performance testing, and the specific test results are shown in the following table:

[0051]

[0052]

[0053] Note: The antifouling test process is as follows: Generally, at least three antifouling tests are conducted. The same location (area is the same) is selected on the tile produced in the embodiment or comparative example (blank group). The tile surface is painted with a blue oil-based pen and then wiped clean with hand washing powder (containing more particles to cause physical friction) (generally, users use conventional detergents to clean tiles, which do not contain particles to abrade the tile surface and are more gentle. The hand washing powder here simulates the situation of excessive cleaning and can better reflect the antifouling effect of the tile); the second time, the same location is painted and wiped clean with hand washing powder; the third time and above are analogous. Among them, "qualified" means that there is basically no mark on the tile surface after naked eye observation; "slight stain absorption" means that the mark on the tile surface is significantly lighter after naked eye observation, and it is not obvious when observed with the naked eye at 1 meter; "severe stain absorption" means that the mark on the tile surface is heavier after naked eye observation, and it is extremely obvious when observed with the naked eye at 1 meter.

[0054] The test results of Example 1 and the blank group show that after applying the wax A of this solution to the polished ceramic tile surface, the initial antifouling performance of the ceramic tile is improved, but the multiple antifouling effect is poor, and the antifouling effect of the ceramic tile decreases after storage for a period of time. The test results of Example 1 and Comparative Example 1 show that compared with conventional antifouling waxes on the market, the antifouling effect of the wax A of this solution is better, but the wax layer will show a small amount of attenuation after storage for a period of time, so the antifouling performance decreases slightly after 6 months.

[0055] Example 2

[0056] The parameters and treatment procedures of this embodiment are consistent with those of Example 1, except that: after applying wax A, wax B is applied;

[0057] By weight, B wax includes the following raw materials: 5 parts of high-viscosity silicone oil (dimethylsiloxane), 4 parts of low-viscosity silicone oil (methylhydrogensiloxane), 3 parts of small molecule silicone oil (methylhydrogenethoxysilane), 8 parts of crosslinking agent (polymethylsiloxane), 4 parts of silane (methylhydrogenethoxysilane), 3 parts of modified silicone nanospheres, 72 parts of solvent (petroleum ether) and 1 part of B wax catalyst (organotin).

[0058] The preparation steps of the modified organic silicon nanoparticles include:

[0059] S01. Dimethylsilane, a crosslinking agent, and trimethylsilane were mixed in a ratio of 4:3:3, and the mixture was sealed and stirred for 10 h to obtain a mixture;

[0060] S02. After adding B wax catalyst (organotin) to the mixture, dilute it with xylene solvent, heat it to 70° C. and react at this temperature for 12 hours to obtain the modified organosilicon microspheres.

[0061] Example 3

[0062] The polished ceramic tile surface of the blank group was waxed: specifically, wax A and wax B were applied to the ceramic tile surface in sequence;

[0063] In parts by weight, the wax A includes the following raw materials: 19 parts of silica sol, 69 parts of solvent (deionized water), 3 parts of high boiling point additive (glycerol), 7 parts of antifouling additive (polyether silicone oil) and 2 parts of coupling agent (silane coupling agent).

[0064] The B wax comprises the following raw materials, in parts by weight: 5 parts of high-viscosity silicone oil (dimethylsiloxane), 4 parts of low-viscosity silicone oil (methylhydrogensiloxane), 3 parts of small molecule silicone oil (methylhydrogenethoxysilane), 8 parts of crosslinking agent (polymethylsiloxane), 4 parts of silane (methylhydrogenethoxysilane), 3 parts of modified organic silicon nanospheres, 72 parts of solvent (petroleum ether) and 1 part of B wax catalyst (organotin);

[0065] The preparation steps of the modified organic silicon nanoparticles include: S01. mixing dimethylsilane, a crosslinking agent, and trimethylsilane in a ratio of 3:2:4, and stirring the mixture in a sealed container for 8 hours to obtain a mixture;

[0066] S02. After adding B wax catalyst (organotin) to the mixture, dilute it with xylene solvent, heat it to 80° C. and react at a constant temperature for 12 hours to obtain the modified organosilicon microspheres.

[0067] Comparative Example 2

[0068] The polished ceramic tile surface of the blank group was waxed: specifically, different wax waters similar to wax A produced in Foshan on the market were applied to the ceramic tile surface; and then different wax waters similar to wax B produced in Foshan on the market were applied.

[0069] Comparative Example 3

[0070] The parameters and treatment procedures of this comparative example are consistent with those of Example 2, with the difference being that wax A in Example 2 is first applied to the surface of the tile, and then a different wax water similar to wax B on the market, produced in Foshan, is applied.

[0071] The waxed tiles of Example 2-3 and Comparative Example 2-3 were subjected to performance testing, and the specific test results are shown in the following table:

[0072]

[0073]

[0074] It can be seen from the test results of Examples 2-3 that after applying wax A on the surface of the ceramic tile, wax B is applied. Since wax B can penetrate into the gaps of wax A and block smaller micropores on the surface of the ceramic tile, the second anti-fouling test result of the ceramic tile is improved to "qualified". Due to the presence of wax B, the protective wax layer formed will not decay even after long-term storage. Therefore, the immediate and long-term anti-fouling effects of the ceramic tile are improved.

[0075] The test results of Comparative Examples 2 and 3 show that directly applying two different commercially available wax solutions similar to Wax A and Wax B does not achieve the same antifouling effect as this solution, and after storage for a period of time, there is a noticeable "fading" phenomenon. Similarly, applying a conventional commercial antifouling wax similar to Wax B on top of Wax A in this solution also produces a poorer antifouling effect than Example 2.

[0076] Example 4

[0077] The parameters and treatment procedures of this embodiment are consistent with those of Example 2, except that: wax A is applied once, wax B is applied once, and wax C is applied once;

[0078] By weight, C wax includes the following raw materials: 10 parts of (low-viscosity) silicone oil (methyl hydrogen siloxane), 5 parts of silane (methyl hydrogen ethoxy silane), 2 parts of C wax catalyst (trifluoromethanesulfonic acid) and 80 parts of solvent (ethanol).

[0079] Example 5

[0080] Waxing treatment is performed on the surface of the ceramic tile. When waxing treatment is performed, wax A, wax B and wax C are applied on the surface of the ceramic tile in sequence;

[0081] By weight, wax A includes the following raw materials: 17 parts of silica sol, 68 parts of solvent (deionized water), 4 parts of high boiling point additive (glycerol), 5 parts of antifouling additive (polyether silicone oil) and 6 parts of coupling agent (silane coupling agent).

[0082] The B wax comprises the following raw materials, in parts by weight: 3 parts of high-viscosity silicone oil (dimethylsiloxane), 3 parts of low-viscosity silicone oil (methylhydrogensiloxane), 4 parts of small molecule silicone oil (methylhydrogenethoxysilane), 6 parts of crosslinking agent (polymethylsiloxane), 5 parts of silane (methylhydrogenethoxysilane), 4 parts of modified organic silicon nanospheres, 73 parts of solvent (petroleum ether) and 2 parts of B wax catalyst (organotin);

[0083] The preparation steps of modified organic silicon nanoparticles include:

[0084] S01. Dimethylsilane, a crosslinking agent, and trimethylsilane were mixed in a ratio of 3.7:2.8:3.5, and the mixture was sealed and stirred for 8 hours to obtain a mixture;

[0085] S02. After adding B wax catalyst to the mixture, dilute it with xylene solvent, heat it to 85° C. and react at this temperature for 12 hours to obtain the modified organosilicon microspheres.

[0086] By weight, C wax includes the following raw materials: 5 parts of (low-viscosity) silicone oil (methyl hydrogen siloxane), 6 parts of silane (methyl hydrogen ethoxy silane), 2 parts of C wax catalyst (trifluoromethanesulfonic acid) and 87 parts of solvent (ethanol).

[0087] Comparative Example 4

[0088] The parameters and treatment procedures of this comparative example are consistent with those of Example 2, except that: wax A and wax B in Example 2 are first applied to the surface of the tile, and then a conventional anti-fouling wax similar to wax C on the market (produced in Foshan, Guangdong) is applied.

[0089] Comparative Example 5

[0090] The polished ceramic tile surfaces of the blank group were waxed: specifically, the conventional first wax water similar to wax A, the second anti-fouling wax similar to wax B, and the third anti-fouling wax similar to wax C on the market were applied to the ceramic tile surfaces in sequence.

[0091] The waxed tiles of Example 4-5 and Comparative Example 4-5 were subjected to performance testing, and the specific test results are shown in the following table:

[0092]

[0093]

[0094] It can be seen from the test results of Examples 4-5 that when A wax and B wax are applied to the surface of the ceramic tile and C wax is applied, since C wax forms a long-term protective film on the previous film layer on the surface of the ceramic tile, the anti-attenuation effect of the ceramic tile is further improved. Therefore, the long-term anti-fouling performance of the ceramic tile is improved, the anti-fouling performance does not decay during storage, and the anti-fouling performance is improved multiple times.

[0095] The test results of Comparative Examples 4 and 5 show that applying a conventional antifouling wax directly over wax A and wax B does not significantly improve long-term antifouling performance, and antifouling performance degrades after storage. When three different commercial waxes / antifouling waxes are directly combined, the antifouling performance of the tiles is poor, and the overall quality is far inferior to the antifouling tiles produced by this solution.

[0096] Example 6

[0097] The various parameters and processing procedures of this embodiment are consistent with those of Example 5, except that the silicone oil of wax B in this embodiment does not simultaneously contain (dimethylsiloxane) high-viscosity silicone oil, low-viscosity silicone oil (methylhydrogensiloxane) and (methylhydrogenethoxysilane) small molecule silicone oil, but is adjusted to use all dimethyl silicone oil.

[0098] Example 7

[0099] The parameters and processing steps of this embodiment are consistent with those of embodiment 5, except that modified organic silicon nanospheres are not added in this embodiment.

[0100] Example 8

[0101] The parameters and processing steps of this embodiment are consistent with those of Example 5, except that the modified organic silicon nanospheres of this embodiment are not subjected to modification treatment, that is, inorganic silicon-silicon dioxide microspheres are directly added.

[0102] The ceramic tiles of Examples 6-8 were subjected to performance tests, and the specific test results are shown in the following table:

[0103]

[0104] From the test results of Example 6, it can be seen that when the silicone oil raw materials in the anti-fouling wax B wax are all the same silicone oil, a good composite effect cannot be achieved, and the anti-attenuation characteristics are weakened. Therefore, the immediate multiple anti-fouling effect and long-term anti-fouling performance are slightly reduced.

[0105] From the test results of Examples 7-8, it can be seen that when the modified organic silicon nanospheres are not introduced into the raw materials, the antifouling performance is also reduced compared with Example 5; when the modified organic silicon nanospheres are not modified, the antifouling performance is also reduced compared with Example 5.

[0106] Example 9

[0107] The parameters and processing steps of this embodiment are consistent with those of embodiment 5, except that the viscosity of the high-viscosity silicone oil is different. For details, see the table below:

[0108] Viscosity / cP Example 5 550 Example 9-1 500 Example 9-2 400 Example 9-3 350 Example 9-4 300 Example 9-5 600

[0109] The ceramic tiles of Example 9 were subjected to performance testing, and the specific test results are shown in the following table:

[0110]

[0111] From the test results of Example 9, it can be seen that the viscosity of the high-viscosity silicone oil in the anti-fouling wax B is preferably 350-550 cP, and most preferably 500 cP. Within the above viscosity range, the immediate anti-fouling performance and long-term anti-fouling effect of the tiles after waxing are relatively optimal.

[0112] Example 10

[0113] The parameters and processing steps of this embodiment are consistent with those of embodiment 5, except that the molecular weight of the small molecule silicone oil is different. For details, see the table below:

[0114]

[0115]

[0116] The ceramic tile of Example 10 was subjected to performance testing, and the specific test results are shown in the following table:

[0117]

[0118] From the test results of Example 10, it can be seen that the molecular weight of the small molecule silicone oil in the anti-fouling wax B is preferably 150-170, and most preferably 161.4. Within the above molecular weight range, the anti-fouling performance of the ceramic tile after waxing is better.

[0119] Example 11

[0120] The parameters and treatment procedures of this embodiment are consistent with those of Example 5, with the only difference being that wax A is applied twice, wax B twice, and wax C once to the tile surface.

[0121] The ceramic tiles of Example 11 were subjected to performance testing, and the specific test results are shown in the following table:

[0122]

[0123] It can be seen from the test results of Example 11 that when the number of applications of A wax and B wax is 2 times, the anti-fouling effect is better than that of Example 5. When the number of applications is increased to 3 or 4 times, the anti-fouling effect will not be significantly improved, and more anti-fouling wax will be consumed. Therefore, the preferred number of applications of A wax and B wax in this scheme is 2 times, and C wax is applied to the outermost layer and only once. During the above-mentioned waxing process, the waxed tiles are stored for 12 months and then subjected to anti-fouling testing. The anti-fouling effect will not decay, and the anti-fouling tiles have a long-term and stable anti-fouling effect.

[0124] Example 12

[0125] Waxing treatment is performed on the surface of the ceramic tile. When waxing treatment is performed, wax A, wax B and wax C are applied on the surface of the ceramic tile in sequence;

[0126] By weight, wax A includes the following raw materials: 19 parts of silica sol, 68 parts of solvent (deionized water), 4 parts of high boiling point additive (propylene glycol), 6 parts of antifouling additive (polyether silicone oil) and 3 parts of coupling agent (silane coupling agent).

[0127] The B wax comprises the following ingredients, by weight: 1-5 parts high-viscosity silicone oil (dimethylsiloxane), 1-5 parts low-viscosity silicone oil (methylhydrogensiloxane), 1-5 parts low-molecule silicone oil (methylhydrogenethoxysilane), 5-10 parts crosslinker (polymethylsiloxane), 1-5 parts silane (methylhydrogenethoxysilane), 1-5 parts modified organosilicon nanospheres, 65-75 parts solvent, and 1-3 parts B wax catalyst. The high-viscosity silicone oil has a viscosity of 500 cP and the low-molecule silicone oil has a molecular weight of 161.4.

[0128] The preparation steps of modified organic silicon nanoparticles include: mixing dimethylsilane, a crosslinker and trimethylsilane in a ratio of 3.7:2.8:3.5, and stirring in a sealed manner for 12 hours to obtain a mixture; adding a catalyst (organotin) to the mixture, and then adding No. 120 solvent oil to dilute it, heating it to 80°C and reacting it at a constant temperature for 24 hours to obtain the modified organic silicon nanoparticles.

[0129] By weight, C wax includes the following raw materials: 8 parts of low-viscosity silicone oil (methyl hydrogen siloxane), 6 parts of silane (methyl hydrogen ethoxy silane), 2 parts of C wax catalyst (trifluoromethanesulfonic acid) and 84 parts of solvent (anhydrous ethanol).

[0130] The ceramic tiles of Example 12 were subjected to performance testing, and the specific test results are shown in the following table:

[0131]

[0132] It can be seen from the test results of Example 12 that after optimizing the raw materials, addition amounts and other parameters of wax A, wax B and wax C, the anti-fouling tiles obtained by this scheme have good immediate and long-term anti-fouling properties. After anti-fouling testing, the anti-fouling effect will not decay even after 12 months of storage.

[0133] Note: As shown in the test results of Example 12 above, the amounts of wax A, wax B and wax C in this solution can be further optimized. In parts by weight, the raw materials and amount of wax A are preferably: 15-20 parts of silica sol, 60-78 parts of solvent, 1-5 parts of high boiling point additive, 5-10 parts of antifouling additive and 1-5 parts of coupling agent; the raw materials and amount of wax B are preferably: 1-5 parts of high viscosity silicone oil (dimethylsiloxane), 1-5 parts of low viscosity silicone oil (methylhydrogensiloxane), 1-5 parts of low viscosity silicone oil (methylhydrogensiloxane), 1-5 parts of high viscosity silicone oil (dimethylsiloxane), 1-5 parts of low viscosity silicone oil (methylhydrogensiloxane), 1-5 parts of high viscosity silicone oil (dimethylsiloxane), 1-5 parts of low viscosity silicone oil (methylhydrogensiloxane), 1-5 parts of high viscosity silicone oil (dimethylsiloxane), 1-5 parts of low viscosity silicone oil (methylhydrogensiloxane), 1-5 parts of high viscosity silicone oil (dimethylsiloxane), 1-5 parts of low viscosity silicone oil (methylhydrogensiloxane), 1-5 parts of high viscosity silicone oil (dimethylsiloxane), 1-5 parts of low viscosity silicone oil (methylhydrogensiloxane), 1-5 parts of high boiling point additive, ... Molecular silicone oil (methylhydrogenethoxysilane) 1-5 parts, crosslinking agent (polymethylsiloxane) 5-10 parts, silane (methylhydrogenethoxysilane) 1-5 parts, modified silicone nanospheres 1-5 parts, solvent 65-75 parts and B wax catalyst 1-3 parts; the raw materials and dosage of C wax are preferably: (low viscosity) silicone oil (methylhydrogenethoxysilane) 5-10 parts, silane (methylhydrogenethoxysilane) 3-8 parts, C wax catalyst 1-3 parts and solvent 79-92 parts.

[0134] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent structural transformations made by using the contents of the present invention specification under the inventive concept of the present invention, or direct / indirect application in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A process for preparing antifouling tiles, characterized in that: The method comprises the following preparation steps: S1. Polishing the tile surface; S2. After waxing the tile surface, the antifouling tile is obtained; During waxing treatment, wax A and wax B are applied to the surface of the tile in sequence; wax A comprises the following raw materials, by weight: 15-20 parts of silica sol, 64-76 parts of solvent, 1-5 parts of grinding aid with a boiling point ≥ 260°C, 3-10 parts of antifouling agent and 1-5 parts of coupling agent; The B wax comprises the following raw materials: 3-15 parts of silicone oil, 5-10 parts of crosslinking agent, 1-5 parts of silane, 1-5 parts of modified organic silicon nanospheres, 65-75 parts of solvent and 1-3 parts of B wax catalyst; The silicone oil comprises at least 10-35% high-viscosity silicone oil and 10-35% low-molecule silicone oil by weight, with the remainder being low-viscosity silicone oil; the viscosity of the high-viscosity silicone oil is 350-550 cP, the viscosity of the low-viscosity silicone oil is 20-50 cP, and the molecular weight of the small-molecule silicone oil is 150-170; The preparation steps of the modified organosilicon nanospheres include: S01. After mixing dimethylsilane, a crosslinking agent and trimethylsilane, the mixture was sealed and stirred for 6-12h to obtain a mixture; S02. Add the B wax catalyst to the mixture, then add a solvent to dilute it, heat it to 60-100° C. and react at a constant temperature for 12 h to 24 h to obtain the modified organosilicon nanospheres.

2. The process for preparing antifouling ceramic tiles according to claim 1, characterized in that: The B wax catalyst is a metal salt.

3. The process for preparing antifouling ceramic tiles according to claim 1, characterized in that: In step S01, the mass ratio of the dimethylsilane, the cross-linking agent and the trimethylsilane is (2-5): (1-4): (2-5).

4. The process for preparing antifouling ceramic tiles according to claim 1, characterized in that: During waxing treatment, A wax, B wax and C wax are applied to the surface of the ceramic tile in sequence; the C wax comprises the following raw materials, in parts by weight: 5-10 parts of methyl hydrogen siloxane, 3-8 parts of silane, 1-3 parts of C wax catalyst and 79-92 parts of solvent; the silane comprises methyl hydrogen ethoxysilane or hexadecyltriethoxysilane.

5. The process for preparing antifouling ceramic tiles according to claim 4, characterized in that: The C wax catalyst is a super acid polymer.

6. The process for preparing antifouling ceramic tiles according to claim 4, characterized in that: Apply A wax twice, B wax twice and C wax once on the tile surface in sequence. 7.An anti-fouling tile, characterized in that: The anti-fouling ceramic tile is prepared by the preparation process of any one of claims 1 to 6.

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