A soft light brick with super anti-fouling coating and preparation method thereof

Abstract

The present invention discloses a soft light brick with a super anti-fouling coating and a preparation method thereof, belonging to the technical field of soft light brick preparation. The preparation method of the soft light brick with a super anti-fouling coating comprises the following steps: Step 1: kaolin, quartz sand, feldspar, clay and a dispersant are mixed, and wet ball milling is performed. After the ball milling is completed, the mixture is allowed to stand to obtain a mixture; Step 2: the mixture is pressed, microwave dried, and sintered to obtain a matrix; Step 3: the matrix is ​​sandblasted, and then a hardener is sprayed, followed by a composite anti-fouling agent sprayed, cured, and polished to obtain a soft light brick with a super anti-fouling coating. The soft light brick prepared by this method has excellent stain resistance, hardness, wear resistance and weather resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of soft light brick preparation, and in particular relates to a soft light brick with a super anti-fouling coating and a preparation method thereof. Background Art

[0002] With the rapid development of society and the continuous improvement of people's living standards, home decoration is no longer limited to aesthetics and practicality, but now places greater emphasis on material durability, cleanability, and environmental performance. As an indispensable component of home decoration, ceramic tiles have become a key focus of industry development, focusing on performance improvement and innovation. Traditional ceramic tile products, whether glossy or matte, have certain limitations. While glossy tiles offer a striking and vibrant decorative effect, they can easily lead to excessive visual stimulation, causing sensory distress, and the problem of light pollution is becoming increasingly prominent. While matte tiles offer low reflectivity, creating a low-key and restrained atmosphere, their lack of reflection can easily create a dull atmosphere, making it difficult to achieve the desired decorative effect. Against this backdrop, soft-light tiles have emerged. They combine the advantages of glossy and matte tiles. Through dynamic soft-light wax polishing technology, they reduce reflectivity and scatter light on the surface, achieving a comfortable visual experience and a light-free decorative effect.

[0003] However, soft-gloss tiles also face some technical challenges, the most prominent of which is their insufficient stain resistance. Because soft-gloss tiles have a moderate surface gloss, they are neither as smooth and easy to clean as bright-finish tiles nor as rough and stain-resistant as matte tiles. Therefore, their stain resistance is relatively weak. In daily use, water stains, oil stains, and other stains easily penetrate the tile surface, making them difficult to clean. This not only affects the tile's aesthetics but also shortens its lifespan.

[0004] Patent CN119409479A discloses a super-fouling-resistant soft-light brick and its preparation method. 60-80 parts of kaolin, 40-60 parts of talc, 20-40 parts of quartz, 20-30 parts of orthoclase, and 15-25 parts of fly ash are placed in a mixer, stirred, ground, molded, and sintered to obtain a green body; ceramic glaze and titanium dioxide are ball-milled with water to obtain glaze slurry, which is then applied to the green body, dried, baked, and polished to form a glaze layer; 5-15 parts of epoxy resin, 4-10 parts of polyurethane resin, 3-8 parts of additives, and 110-120 parts of diluent are mixed, applied to the surface of the glaze layer, cured to form a protective coating, and then the brick is made. Fluorine-containing additives, quaternary ammonium salt structures, and silaneoxy groups are stably present in the protective coating, while the glaze layer contains titanium dioxide, and the coating and glaze layers have good adhesion. The two interact with the green body to make the bricks of the present invention excellent and stable in hydrophobicity, antibacterial properties, and light-softening properties. However, the stain resistance, hardness, wear resistance, and weather resistance of the bricks prepared by this method still have room for improvement. Summary of the Invention

[0005] The purpose of the present invention is to provide a soft light brick with a super anti-fouling coating and a preparation method thereof, so as to solve the technical problems of poor stain resistance, hardness, wear resistance and weather resistance of soft light bricks in the prior art.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] The present invention provides a method for preparing a soft light brick with a super anti-fouling coating, comprising the following steps:

[0008] Step 1: Mix kaolin, quartz sand, feldspar, clay and dispersant, and use wet ball milling. After the ball milling is completed, let it stand to obtain a mixture;

[0009] Step 2: Pressing the mixture, drying it with microwaves, and sintering it to obtain a matrix;

[0010] Step 3: sandblast the substrate, then spray a hardening agent, and then spray a composite antifouling agent, solidify, and polish to obtain a soft light brick with a super antifouling coating.

[0011] Preferably, in step 1, the dosage ratio of kaolin, quartz sand, feldspar, clay and dispersant is (40-50) g: (22-28) g: (18-23) g: (8-13) g: (0.4-0.8) g. During the wet ball milling process, the ball-to-material ratio is 2:1, zirconia balls are used as the grinding medium, and the mill is ground at 300-500 rpm for 4-6 h. The slurry fineness is controlled to be ≤5 μm, and the mill is allowed to stand at 25° C. for 40-50 h.

[0012] Preferably, in the step 2, during the pressing process, the pressure is maintained at 30-35 MPa for 110-140 seconds, the microwave drying frequency is 2.45 GHz, and the sintering process is: heating from room temperature to 300°C at a heating rate of 3°C / min, keeping warm for 30-45 minutes, then heating from 300°C to 1180°C at a heating rate of 5°C / min, keeping warm for 80-100 minutes, and then naturally cooling to 200-220°C before being taken out of the furnace; in the step 3, during the sandblasting treatment, 120 mesh corundum sand is used, the compressed air pressure is 0.5-0.8 MPa, and the spray distance is 20-30 cm.

[0013] Preferably, the preparation method of the hardener comprises the following steps:

[0014] Q1: In an ice bath, phosphorus oxychloride was added dropwise to N,N-dimethylformamide. After the addition was complete, the mixture was stirred at room temperature to obtain a mixed solution 1. 2,7-Dimethoxynaphthalene was then added to dichloromethane and stirred to dissolve to obtain a mixed solution 2. The mixed solution 1 was added dropwise to the mixed solution 2. After the addition was complete, the mixture was stirred at room temperature. The mixture was then added to deionized water, stirred, the pH was adjusted, extraction was performed, drying was performed, vacuum rotary evaporation was performed, recrystallization was performed, and vacuum drying was performed to obtain intermediate 1.

[0015] Q2: Add intermediate 1 to dichloromethane, slowly add boron tribromide solution dropwise under nitrogen and ice bath, stir and react at room temperature after the addition is complete, add the product dropwise to a container filled with deionized water under ice bath, continue stirring and react at room temperature after the addition is complete, adjust the pH, extract, dry, evaporate under reduced pressure, and purify to obtain intermediate 2;

[0016] Q3: Under a nitrogen atmosphere, diglycolic acid was added to the acid anhydride, heated with stirring to reflux, and phosphoric acid was added to catalyze the reaction. After the reaction, the product was evaporated under reduced pressure, concentrated, crystallized at low temperature, and filtered to obtain intermediate 3. Pyrrolidine was added to a container containing dichloromethane, followed by intermediate 3, and the reaction was stirred at room temperature. After the reaction, the product was evaporated under reduced pressure and crystallized at low temperature to obtain intermediate 4.

[0017] Q4: Add intermediate 2 to N,N-dimethylformamide, add intermediate 4 under stirring, then add concentrated sulfuric acid dropwise, heat and stir to react, extract, adjust pH, extract, dry, concentrate by distillation under reduced pressure, and purify to obtain a hardener.

[0018] In the above process, the synthetic reaction formula of the hardener is as follows:

[0019]

[0020] The results of mass spectrometry analysis of intermediate 1 were: m / z: 216.08 (100.0%), 217.08 (14.3%); the results of mass spectrometry analysis of intermediate 2 were: m / z: 188.05 (100.0%), 189.05 (12.1%), 190.05 (1.3%); the results of mass spectrometry analysis of intermediate 3 were: m / z: 116.01 (100.0%), 117.01 (4.3%); the results of mass spectrometry analysis of intermediate 4 were: m / z: 187.08 (100.0%), 188.09 (9.0%), 189.09 (1.2%); the results of mass spectrometry analysis of the hardener were: m / z: 526.20 (100.0%), 527.20 (29.9%), 528.20 (6.4%).

[0021] Preferably, in Q1, the usage ratio of phosphorus oxychloride, N,N-dimethylformamide, 2,7-dimethoxynaphthalene and dichloromethane is (8-10) mL: (3-5) mL: (2-3) g: (10-12) mL; in Q2, the usage ratio of intermediate 1, dichloromethane and boron tribromide solution is (0.45-0.65) g: (8-10) mL: (5-7) mL, and the concentration of boron tribromide solution is 0.526 g / mL.

[0022] Preferably, in Q3, the usage ratio of diglycolic acid, acid anhydride and phosphoric acid is (45-55) g: (120-145) mL: (0.07-0.09) mL; the usage ratio of pyrrolidine, dichloromethane and intermediate 3 is (10.2-11.4) g: (140-160) mL: (17.1-17.8) g; and in Q4, the usage ratio of intermediate 2, N,N-dimethylformamide, intermediate 4 and concentrated sulfuric acid is (2.068-2.124) g: (20-25) mL: (3.5-3.83) g: (0.03-0.04) g.

[0023] Preferably, the preparation method of the composite antifouling agent comprises the following steps:

[0024] S1: n-Dodecanethiol, methyltrioctyl ammonium chloride, and acetone are added to a reaction vessel in sequence under an ice bath, followed by dropwise addition of sodium hydroxide solution and stirring, followed by addition of acetone and carbon disulfide, reaction, and then addition of chloroform and sodium hydroxide solution. After the addition is complete, stirring is carried out under ice bath, and purification is performed after the stirring is completed to obtain product A;

[0025] S2: 4-vinylbenzyl chloride and triphenylphosphine are sequentially added to a container containing acetone, stirred, vacuumed, and then heated for reaction. After the reaction is completed, the mixture is settled, washed, vacuum filtered, and dried to obtain product B;

[0026] S3: Add product A, product B and methanol to a container in sequence, then add azobisisobutyronitrile, stir, evacuate, heat to react, place in liquid nitrogen environment to quench the reaction, freeze, dialyze, and vacuum dry to obtain product C; add product C, divinylbenzene, methanol and azobisisobutyronitrile to a container in sequence, stir to react, evacuate, heat to react, place in liquid nitrogen to quench the reaction, settle, and purify to obtain a composite antifouling agent.

[0027] In the above process, n-dodecanethiol undergoes a nucleophilic addition reaction with carbon disulfide under alkaline conditions, followed by a nucleophilic substitution reaction with chloroform to obtain product A. Product B is prepared using 4-vinylbenzyl chloride and triphenylphosphine as raw materials. Then, product A and product B undergo RAFT polymerization with azobisisobutyronitrile as an initiator to obtain product C. Subsequently, product C undergoes RAFT polymerization with divinylbenzene to obtain a composite antifouling agent.

[0028] Preferably, in S1, the usage ratio of n-dodecanethiol, methyltrioctylammonium chloride, carbon disulfide and chloroform is (20.12-20.4) g: (0.98-1.05) g: (7.2-8.1) g: (17.12-18.74) g; and in S2, the usage ratio of 4-vinylbenzyl chloride, triphenylphosphine and acetone is (9.01-9.32) g: (18.45-19.12) g: (90-120) mL.

[0029] Preferably, in S3, the usage ratio of product A, product B, methanol and azobisisobutyronitrile is (4.01-4.33) g: (0.08-0.1) g: (12-15) mL: (0.02-0.05) g; the usage ratio of product C, divinylbenzene, methanol and azobisisobutyronitrile is (0.01-0.032) g: (0.028-0.034) g: (4-6) mL: (0.002-0.005) g.

[0030] Preferably, a soft light brick with a super anti-fouling coating is prepared by the method for preparing a soft light brick with a super anti-fouling coating.

[0031] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0032] 1. The present invention first uses phosphorus oxychloride, 2,7-dimethoxynaphthalene, boron tribromide solution, diglycolic acid and pyrrolidine as main raw materials to prepare a hardener, and then uses n-dodecyl mercaptan, carbon disulfide, methyltrioctylammonium chloride, 4-vinylbenzyl chloride, triphenylphosphine and divinylbenzene as main raw materials to prepare a composite anti-fouling agent. Adding the hardener and the composite anti-fouling agent to the preparation process of soft light bricks can effectively improve their hardness, weather resistance, anti-fouling performance, wear resistance and self-repairing performance.

[0033] 2. The present invention adds the prepared hardener to the preparation process of the soft light brick, which can effectively improve its hardness, wear resistance and weather resistance. The naphthalene ring contained in the hardener has extremely high rigidity, forming a molecular scaffold in the soft light brick, restricting the movement of polymer chain segments, and improving the overall hardness of the soft light brick. The carbonyl and hydroxyl groups contained in the hardener form a hydrogen bond network, enhancing the interfacial bonding force, and thus improving the hardness. The nitrogen atoms in the five-membered heterocyclic ring can participate in the electron cloud delocalization of the soft light brick matrix to form a flexible buffer layer, disperse local stress, and improve wear resistance. At the same time, the ether bonds contained in the hardener are hydrophobic, reduce moisture penetration, inhibit the expansion and contraction of the matrix caused by hydration, and improve weather resistance.

[0034] 3. The present invention adds the prepared composite anti-fouling agent to the preparation process of soft light bricks, which can effectively improve their anti-fouling performance, wear resistance and self-repairing performance. The long-chain alkyl contained in the composite anti-fouling agent can form a hydrophobic layer on the surface of the soft light brick, reduce surface energy, and reduce the adsorption of water molecules and oily pollutants. At the same time, the benzene ring structure contained can form a dense shielding layer on the surface of the soft light layer, flame retardant The penetration of corrosive ions makes the soft light brick have excellent anti-fouling performance. The cross-linked structure contained in the composite anti-fouling agent can absorb impact energy and improve wear resistance. The presence of disulfide bonds can break and reorganize under the action of light or heat, repair surface cracks, and improve its self-repairing ability. DETAILED DESCRIPTION

[0035] 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. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0036] Example 1: This example discloses a method for preparing a hardener, comprising the following steps:

[0037] Q1: In an ice bath, 9 mL of phosphorus oxychloride was added dropwise to 4 mL of N,N-dimethylformamide. After the addition was complete, the mixture was stirred at room temperature for 30 min to obtain a mixed solution 1. 2.5 g of 2,7-dimethoxynaphthalene was then added to 11 mL of dichloromethane and stirred to dissolve to obtain a mixed solution 2. The mixed solution 1 was added dropwise to the mixed solution 2. After the addition was complete, the mixture was stirred at room temperature for 10 h. The mixture was then added to 300 mL of deionized water and stirred for 3 h. The pH was adjusted to 7 with a saturated sodium bicarbonate solution. The mixture was extracted with dichloromethane, dried, evaporated under reduced pressure, recrystallized, and dried in vacuo to obtain intermediate 1.

[0038] Q2: 0.55 g of intermediate 1 was added to 9 mL of dichloromethane. Under nitrogen and an ice bath, 6 mL of a 0.526 g / mL boron tribromide solution was slowly added dropwise. After the addition was complete, the reaction was stirred at room temperature for 12 h. After the reaction was complete, the product was added dropwise to a container containing 100 mL of deionized water under an ice bath. After the addition was complete, the reaction was continued with stirring at room temperature for 3 h. The pH was adjusted to 7 with a saturated sodium bicarbonate solution, and the product was extracted with dichloromethane, dried, and purified by vacuum rotary evaporation to obtain intermediate 2.

[0039] Q3: Under a nitrogen atmosphere, 50 g of diglycolic acid was added to 132 mL of acid anhydride, heated with stirring and refluxed for 10 h. After reflux, 0.08 mL of phosphoric acid was added to catalyze the reaction for 2 h. After the reaction, the product was evaporated under reduced pressure, concentrated, crystallized at low temperature, and filtered to obtain intermediate 3. 10.8 g of pyrrolidine was added to a container containing 150 mL of dichloromethane, followed by the addition of 17.4 g of intermediate 3. The product was stirred at room temperature for 2 h. After the reaction, the product was evaporated under reduced pressure and crystallized at low temperature to obtain intermediate 4.

[0040] Q4: Add 2.086 g of intermediate 2 to 22.5 mL of N,N-dimethylformamide, add 3.61 g of intermediate 4 under stirring, then add dropwise 0.035 g of 98 wt% concentrated sulfuric acid, heat and stir at 45°C for 6 h, extract, adjust the pH, extract, dry, concentrate by distillation under reduced pressure, and purify to obtain a hardener.

[0041] This embodiment discloses a method for preparing a composite antifouling agent, comprising the following steps:

[0042] S1: In an ice bath, 20.27 g of n-dodecanethiol, 1.02 g of methyltrioctylammonium chloride, and 55 g of acetone were sequentially added to a reaction vessel, followed by dropwise addition of 20 mL of a 50 wt% sodium hydroxide solution, followed by stirring for 20 min, followed by addition of 10 g of acetone and 7.6 g of carbon disulfide, followed by reaction, and then addition of 17.93 g of chloroform and 40 mL of a 50 wt% sodium hydroxide solution. After the addition was complete, the mixture was stirred in an ice bath for 12 h. After the stirring was completed, the mixture was purified to obtain product A.

[0043] S2: 9.16 g of 4-vinylbenzyl chloride and 18.83 g of triphenylphosphine were added sequentially to a container containing 105 mL of acetone, stirred for 10 min, and then evacuated and heated at 62°C for 48 h. After the reaction, the mixture was settled, washed, vacuum filtered, and dried to obtain product B.

[0044] S3: 4.17 g of product A, 0.09 g of product B and 13.5 mL of methanol were added to the container in sequence, and then 0.035 g of azobisisobutyronitrile was added, stirred for 10 min, vacuumed, heated at 65 ° C for 20 h, placed in a liquid nitrogen environment to quench the reaction, frozen, dialyzed, and vacuum dried to obtain product C; 0.021 g of product C, 0.031 g of divinylbenzene, 5 mL of methanol and 0.003 g of azobisisobutyronitrile were added to the container in sequence, stirred for 10 min, vacuumed, heated at 70 ° C for 15 h, placed in liquid nitrogen to quench the reaction, settled, and purified to obtain a composite anti-fouling agent.

[0045] This embodiment discloses a method for preparing a soft light brick with a super anti-fouling coating, comprising the following steps:

[0046] Step 1: 45 g of kaolin, 25 g of quartz sand, 20.5 g of feldspar, 10.5 g of clay and 0.6 g of dispersant were mixed and wet ball milled. During the wet ball milling process, the ball-to-material ratio was 2:1, zirconia balls were used as grinding media, and the mixture was milled at 300-500 rpm for 6 h. The slurry fineness was controlled to be ≤5 μm. After the ball milling was completed, the mixture was allowed to stand at 25°C for 48 h to obtain a mixture.

[0047] Step 2: The mixture was pressed at 35 MPa for 120 seconds, dried by 2.45 GHz microwave, and sintered. The sintering process was as follows: heating from room temperature to 300°C at a heating rate of 3°C / min, holding for 45 minutes, then heating from 300°C to 1180°C at a heating rate of 5°C / min, holding for 90 minutes, and then naturally cooled to 200°C before being taken out of the furnace to obtain the matrix;

[0048] Step 3: Sandblast the substrate with 120-mesh corundum sand, with a compressed air pressure of 0.6 MPa and a spray distance of 25 cm. Then spray the hardener, followed by the composite anti-fouling agent, cure, and polish to obtain a soft light brick with a super anti-fouling coating.

[0049] Example 2: This example discloses a method for preparing a hardener, comprising the following steps:

[0050] Q1: In an ice bath, 8 mL of phosphorus oxychloride was added dropwise to 5 mL of N,N-dimethylformamide. After the addition was complete, the mixture was stirred at room temperature for 30 min to obtain a mixed solution 1. 3 g of 2,7-dimethoxynaphthalene was then added to 10 mL of dichloromethane and stirred to dissolve to obtain a mixed solution 2. The mixed solution 1 was added dropwise to the mixed solution 2, and the mixture was stirred at room temperature for 10 h. The mixture was then added to 300 mL of deionized water and stirred for 3 h. The pH was adjusted to 7 with a saturated sodium bicarbonate solution, and the mixture was extracted with dichloromethane, dried, evaporated under reduced pressure, recrystallized, and dried in vacuo to obtain intermediate 1.

[0051] Q2: 0.45 g of intermediate 1 was added to 10 mL of dichloromethane. Under nitrogen and an ice bath, 5 mL of a 0.526 g / mL boron tribromide solution was slowly added dropwise. After the addition was complete, the reaction was stirred at room temperature for 12 hours. After the reaction was complete, the product was added dropwise to a container containing 100 mL of deionized water under an ice bath. After the addition was complete, the reaction was continued with stirring at room temperature for 3 hours. The pH was adjusted to 7 with a saturated sodium bicarbonate solution, and the product was extracted with dichloromethane, dried, and purified by vacuum rotary evaporation to obtain intermediate 2.

[0052] Q3: Under a nitrogen atmosphere, 45 g of diglycolic acid was added to 120 mL of acid anhydride, heated with stirring and refluxed for 10 h. After reflux, 0.09 mL of phosphoric acid was added to catalyze the reaction for 2 h. After the reaction, the product was evaporated under reduced pressure, concentrated, crystallized at low temperature, and filtered to obtain intermediate 3. 10.2 g of pyrrolidine was added to a container containing 140 mL of dichloromethane, followed by the addition of 17.1 g of intermediate 3. The product was stirred at room temperature for 2 h. After the reaction, the product was evaporated under reduced pressure and crystallized at low temperature to obtain intermediate 4.

[0053] Q4: 2.068 g of intermediate 2 was added to 20 mL of N,N-dimethylformamide, 3.5 g of intermediate 4 was added under stirring, and then 0.03 g of 98 wt% concentrated sulfuric acid was added dropwise. The mixture was heated and stirred at 45°C for 6 h, extracted, adjusted the pH, extracted again, dried, concentrated by vacuum distillation, and purified to obtain a hardener.

[0054] This embodiment discloses a method for preparing a composite antifouling agent, comprising the following steps:

[0055] S1: In an ice bath, 20.12 g of n-dodecanethiol, 0.98 g of methyltrioctylammonium chloride, and 55 g of acetone were sequentially added to a reaction vessel, followed by dropwise addition of 20 mL of a 50 wt% sodium hydroxide solution, and stirring for 20 min. 10 g of acetone and 7.2 g of carbon disulfide were then added and reacted. 17.12 g of chloroform and 40 mL of a 50 wt% sodium hydroxide solution were then added. After the addition was complete, the mixture was stirred in an ice bath for 12 h. After the stirring was complete, the mixture was purified to obtain product A.

[0056] S2: 9.01 g of 4-vinylbenzyl chloride and 18.45 g of triphenylphosphine were added sequentially to a container containing 90 mL of acetone, stirred for 10 min, and then evacuated and heated at 62°C for 48 h. After the reaction, the mixture was settled, washed, vacuum filtered, and dried to obtain product B.

[0057] S3: 4.01 g of product A, 0.1 g of product B and 15 mL of methanol were added to the container in sequence, and then 0.02 g of azobisisobutyronitrile was added, stirred for 10 min, vacuumed, heated at 65 ° C for 20 h, placed in a liquid nitrogen environment to quench the reaction, frozen, dialyzed, and vacuum dried to obtain product C; 0.01 g of product C, 0.028 g of divinylbenzene, 4 mL of methanol and 0.002 g of azobisisobutyronitrile were added to the container in sequence, stirred for 10 min, vacuumed, heated at 70 ° C for 15 h, placed in liquid nitrogen to quench the reaction, settled, and purified to obtain a composite anti-fouling agent.

[0058] This embodiment discloses a method for preparing a soft light brick with a super anti-fouling coating, comprising the following steps:

[0059] Step 1: 40 g of kaolin, 22 g of quartz sand, 18 g of feldspar, 8 g of clay and 0.4 g of dispersant were mixed and wet ball milled. During the wet ball milling process, the ball-to-material ratio was 2:1, zirconia balls were used as the grinding medium, and the mixture was milled at 300-500 rpm for 6 h. The slurry fineness was controlled to be ≤5 μm. After the ball milling was completed, the mixture was allowed to stand at 25°C for 48 h to obtain a mixture.

[0060] Step 2: The mixture was pressed at 35 MPa for 120 seconds, dried by 2.45 GHz microwave, and sintered. The sintering process was as follows: heating from room temperature to 300°C at a heating rate of 3°C / min, holding for 45 minutes, then heating from 300°C to 1180°C at a heating rate of 5°C / min, holding for 90 minutes, and then naturally cooled to 200°C before being taken out of the furnace to obtain the matrix;

[0061] Step 3: Sandblast the substrate with 120-mesh corundum sand, with a compressed air pressure of 0.6 MPa and a spray distance of 25 cm. Then spray the hardener, followed by the composite anti-fouling agent, cure, and polish to obtain a soft light brick with a super anti-fouling coating.

[0062] Example 3: This example discloses a method for preparing a hardener, comprising the following steps:

[0063] Q1: In an ice bath, 10 mL of phosphorus oxychloride was added dropwise to 3 mL of N,N-dimethylformamide. After the addition was complete, the mixture was stirred at room temperature for 30 min to obtain a mixed solution 1. 2 g of 2,7-dimethoxynaphthalene was then added to 12 mL of dichloromethane and stirred to dissolve to obtain a mixed solution 2. The mixed solution 1 was added dropwise to the mixed solution 2, and the mixture was stirred at room temperature for 10 h. The mixture was then added to 300 mL of deionized water and stirred for 3 h. The pH was adjusted to 7 with a saturated sodium bicarbonate solution, and the mixture was extracted with dichloromethane, dried, evaporated under reduced pressure, recrystallized, and dried in vacuo to obtain intermediate 1.

[0064] Q2: 0.65 g of intermediate 1 was added to 8 mL of dichloromethane. Under nitrogen and an ice bath, 7 mL of a 0.526 g / mL boron tribromide solution was slowly added dropwise. After the addition was complete, the reaction was stirred at room temperature for 12 h. After the reaction was complete, the product was added dropwise to a container containing 100 mL of deionized water under an ice bath. After the addition was complete, the reaction was continued with stirring at room temperature for 3 h. The pH was adjusted to 7 with a saturated sodium bicarbonate solution, and the product was extracted with dichloromethane, dried, and purified by vacuum rotary evaporation to obtain intermediate 2.

[0065] Q3: Under a nitrogen atmosphere, 55 g of diglycolic acid was added to 145 mL of acid anhydride, heated with stirring and refluxed for 10 h. After reflux, 0.07 mL of phosphoric acid was added to catalyze the reaction for 2 h. After the reaction, the product was evaporated under reduced pressure, concentrated, crystallized at low temperature, and filtered to obtain intermediate 3. 11.4 g of pyrrolidine was added to a container containing 160 mL of dichloromethane, followed by the addition of 17.8 g of intermediate 3. The product was stirred at room temperature for 2 h. After the reaction, the product was evaporated under reduced pressure and crystallized at low temperature to obtain intermediate 4.

[0066] Q4: Add 2.124 g of intermediate 2 to 25 mL of N,N-dimethylformamide, add 3.83 g of intermediate 4 under stirring, then add dropwise 0.04 g of 98 wt% concentrated sulfuric acid, heat and stir at 45°C for 6 h, extract, adjust the pH, extract, dry, concentrate by distillation under reduced pressure, and purify to obtain a hardener.

[0067] This embodiment discloses a method for preparing a composite antifouling agent, comprising the following steps:

[0068] S1: In an ice bath, 20.4 g of n-dodecanethiol, 1.05 g of methyltrioctylammonium chloride, and 55 g of acetone were sequentially added to a reaction vessel, followed by dropwise addition of 20 mL of a 50 wt% sodium hydroxide solution, followed by stirring for 20 min, followed by addition of 10 g of acetone and 8.1 g of carbon disulfide, and reaction. 18.74 g of chloroform and 40 mL of a 50 wt% sodium hydroxide solution were then added. After the addition was complete, the mixture was stirred in an ice bath for 12 h. After the stirring was completed, the mixture was purified to obtain product A.

[0069] S2: 9.32 g of 4-vinylbenzyl chloride and 19.12 g of triphenylphosphine were added sequentially to a container containing 120 mL of acetone, stirred for 10 min, and then evacuated and heated at 62°C for 48 h. After the reaction, the mixture was settled, washed, vacuum filtered, and dried to obtain product B.

[0070] S3: 4.33 g of product A, 0.08 g of product B and 12 mL of methanol were added to the container in sequence, and then 0.05 g of azobisisobutyronitrile was added, stirred for 10 min, vacuumed, heated at 65 ° C for 20 h, placed in a liquid nitrogen environment to quench the reaction, frozen, dialyzed, and vacuum dried to obtain product C; 0.032 g of product C, 0.034 g of divinylbenzene, 6 mL of methanol and 0.005 g of azobisisobutyronitrile were added to the container in sequence, stirred for 10 min, vacuumed, heated at 70 ° C for 15 h, placed in liquid nitrogen to quench the reaction, settled, and purified to obtain a composite anti-fouling agent.

[0071] This embodiment discloses a method for preparing a soft light brick with a super anti-fouling coating, comprising the following steps:

[0072] Step 1: 50 g of kaolin, 28 g of quartz sand, 23 g of feldspar, 13 g of clay and 0.8 g of dispersant were mixed and wet ball milled. During the wet ball milling process, the ball-to-material ratio was 2:1, zirconia balls were used as grinding media, and the mixture was milled at 300-500 rpm for 6 h. The slurry fineness was controlled to be ≤5 μm. After the ball milling was completed, the mixture was allowed to stand at 25°C for 48 h to obtain a mixture.

[0073] Step 2: The mixture was pressed at 35 MPa for 120 seconds, dried by 2.45 GHz microwave, and sintered. The sintering process was as follows: heating from room temperature to 300°C at a heating rate of 3°C / min, holding for 45 minutes, then heating from 300°C to 1180°C at a heating rate of 5°C / min, holding for 90 minutes, and then naturally cooled to 200°C before being taken out of the furnace to obtain the matrix;

[0074] Step 3: Sandblast the substrate with 120-mesh corundum sand, with a compressed air pressure of 0.6 MPa and a spray distance of 25 cm. Then spray the hardener, followed by the composite anti-fouling agent, cure, and polish to obtain a soft light brick with a super anti-fouling coating.

[0075] Example 4: This example discloses a method for preparing a hardener, comprising the following steps:

[0076] Q1: In an ice bath, 8.5 mL of phosphorus oxychloride was added dropwise to 3.2 mL of N,N-dimethylformamide. After the addition was complete, the mixture was stirred at room temperature for 30 min to obtain a mixed solution 1. 2.1 g of 2,7-dimethoxynaphthalene was then added to 10.5 mL of dichloromethane and stirred to dissolve to obtain a mixed solution 2. The mixed solution 1 was added dropwise to the mixed solution 2. After the addition was complete, the mixture was stirred at room temperature for 10 h. The mixture was then added to 300 mL of deionized water and stirred for 3 h. The pH was adjusted to 7 with a saturated sodium bicarbonate solution. The mixture was extracted with dichloromethane, dried, evaporated under reduced pressure, recrystallized, and dried in vacuo to obtain intermediate 1.

[0077] Q2: 0.5 g of intermediate 1 was added to 8.5 mL of dichloromethane. Under nitrogen and an ice bath, 6.5 mL of a 0.526 g / mL boron tribromide solution was slowly added dropwise. After the addition was complete, the reaction was stirred at room temperature for 12 hours. After the reaction was complete, the product was added dropwise to a container containing 100 mL of deionized water under an ice bath. After the addition was complete, the reaction was continued with stirring at room temperature for 3 hours. The pH was adjusted to 7 with a saturated sodium bicarbonate solution, and the product was extracted with dichloromethane, dried, and purified by vacuum rotary evaporation to obtain intermediate 2.

[0078] Q3: Under a nitrogen atmosphere, 48 g of diglycolic acid was added to 128 mL of acid anhydride, heated with stirring and refluxed for 10 h. After reflux, 0.075 mL of phosphoric acid was added to catalyze the reaction for 2 h. After the reaction, the product was evaporated under reduced pressure, concentrated, crystallized at low temperature, and filtered to obtain intermediate 3. 10.5 g of pyrrolidine was added to a container containing 145 mL of dichloromethane, followed by the addition of 17.3 g of intermediate 3. The product was stirred at room temperature for 2 h. After the reaction, the product was evaporated under reduced pressure and crystallized at low temperature to obtain intermediate 4.

[0079] Q4: Add 2.073 g of intermediate 2 to 22 mL of N,N-dimethylformamide, add 3.55 g of intermediate 4 under stirring, then add dropwise 0.032 g of 98 wt% concentrated sulfuric acid, heat and stir at 45°C for 6 h, extract, adjust the pH, extract, dry, concentrate by distillation under reduced pressure, and purify to obtain a hardener.

[0080] This embodiment discloses a method for preparing a composite antifouling agent, comprising the following steps:

[0081] S1: In an ice bath, 20.18 g of n-dodecyl mercaptan, 1.01 g of methyltrioctylammonium chloride, and 55 g of acetone were sequentially added to a reaction vessel, followed by dropwise addition of 20 mL of a 50 wt% sodium hydroxide solution, and stirring for 20 min. 10 g of acetone and 7.4 g of carbon disulfide were then added and reacted. 17.51 ​​g of chloroform and 40 mL of a 50 wt% sodium hydroxide solution were then added. After the addition was complete, the mixture was stirred in an ice bath for 12 h. After the stirring was completed, the mixture was purified to obtain product A.

[0082] S2: 9.08 g of 4-vinylbenzyl chloride and 18.62 g of triphenylphosphine were added sequentially to a container containing 95 mL of acetone, stirred for 10 min, and then evacuated and heated at 62°C for 48 h. After the reaction, the mixture was settled, washed, vacuum filtered, and dried to obtain product B.

[0083] S3: 4.09 g of product A, 0.085 g of product B and 14 mL of methanol were added to the container in sequence, and then 0.03 g of azobisisobutyronitrile was added, stirred for 10 min, vacuumed, heated at 65 ° C for 20 h, placed in a liquid nitrogen environment to quench the reaction, frozen, dialyzed, and vacuum dried to obtain product C; 0.018 g of product C, 0.029 g of divinylbenzene, 4.5 mL of methanol and 0.004 g of azobisisobutyronitrile were added to the container in sequence, stirred for 10 min, vacuumed, heated at 70 ° C for 15 h, placed in liquid nitrogen to quench the reaction, settled, and purified to obtain a composite anti-fouling agent.

[0084] This embodiment discloses a method for preparing a soft light brick with a super anti-fouling coating, comprising the following steps:

[0085] Step 1: 42 g of kaolin, 23 g of quartz sand, 19 g of feldspar, 9 g of clay and 0.5 g of dispersant were mixed and wet ball milled. During the wet ball milling process, the ball-to-material ratio was 2:1, zirconia balls were used as grinding media, and the mixture was milled at 300-500 rpm for 6 h. The slurry fineness was controlled to be ≤5 μm. After the ball milling was completed, the mixture was allowed to stand at 25°C for 48 h to obtain a mixture.

[0086] Step 2: The mixture was pressed at 35 MPa for 120 seconds, dried by 2.45 GHz microwave, and sintered. The sintering process was as follows: heating from room temperature to 300°C at a heating rate of 3°C / min, holding for 45 minutes, then heating from 300°C to 1180°C at a heating rate of 5°C / min, holding for 90 minutes, and then naturally cooled to 200°C before being taken out of the furnace to obtain the matrix;

[0087] Step 3: Sandblast the substrate with 120-mesh corundum sand, with a compressed air pressure of 0.6 MPa and a spray distance of 25 cm. Then spray the hardener, followed by the composite anti-fouling agent, cure, and polish to obtain a soft light brick with a super anti-fouling coating.

[0088] Example 5: This example discloses a method for preparing a hardener, comprising the following steps:

[0089] Q1: In an ice bath, 9.5 mL of phosphorus oxychloride was added dropwise to 4.8 mL of N,N-dimethylformamide. After the addition was complete, the mixture was stirred at room temperature for 30 min to obtain a mixed solution 1. 2.9 g of 2,7-dimethoxynaphthalene was then added to 11.5 mL of dichloromethane and stirred to dissolve to obtain a mixed solution 2. The mixed solution 1 was added dropwise to the mixed solution 2. After the addition was complete, the mixture was stirred at room temperature for 10 h. The mixture was then added to 300 mL of deionized water and stirred for 3 h. The pH was adjusted to 7 with a saturated sodium bicarbonate solution. The mixture was extracted with dichloromethane, dried, evaporated under reduced pressure, recrystallized, and dried in vacuo to obtain intermediate 1.

[0090] Q2: 0.6 g of intermediate 1 was added to 9.5 mL of dichloromethane. Under nitrogen and ice bath conditions, 7.5 mL of 0.526 g / mL boron tribromide solution was slowly added dropwise. After the addition was complete, the reaction was stirred at room temperature for 12 hours. After the reaction was complete, the product was added dropwise to a container containing 100 mL of deionized water under ice bath conditions. After the addition was complete, the reaction was continued with stirring at room temperature for 3 hours. The pH was adjusted to 7 with saturated sodium bicarbonate solution, and the product was extracted with dichloromethane, dried, and purified by vacuum rotary evaporation to obtain intermediate 2.

[0091] Q3: Under a nitrogen atmosphere, 52 g of diglycolic acid was added to 141 mL of acid anhydride, heated with stirring and refluxed for 10 h. After reflux, 0.085 mL of phosphoric acid was added to catalyze the reaction for 2 h. After the reaction, the product was evaporated under reduced pressure, concentrated, crystallized at low temperature, and filtered to obtain intermediate 3. 11.1 g of pyrrolidine was added to a container containing 155 mL of dichloromethane, followed by the addition of 17.6 g of intermediate 3. The product was stirred at room temperature for 2 h. After the reaction, the product was evaporated under reduced pressure and crystallized at low temperature to obtain intermediate 4.

[0092] Q4: Add 2.095 g of intermediate 2 to 24 mL of N,N-dimethylformamide, add 3.71 g of intermediate 4 under stirring, then add dropwise 0.038 g of 98 wt% concentrated sulfuric acid, heat and stir at 45°C for 6 h, extract, adjust the pH, extract, dry, concentrate by distillation under reduced pressure, and purify to obtain a hardener.

[0093] This embodiment discloses a method for preparing a composite antifouling agent, comprising the following steps:

[0094] S1: In an ice bath, 20.33 g of n-dodecanethiol, 1.03 g of methyltrioctylammonium chloride, and 55 g of acetone were sequentially added to a reaction vessel, followed by dropwise addition of 20 mL of a 50 wt% sodium hydroxide solution, followed by stirring for 20 min, followed by addition of 10 g of acetone and 8 g of carbon disulfide, followed by reaction, and then addition of 18.53 g of chloroform and 40 mL of a 50 wt% sodium hydroxide solution. After the addition was complete, the mixture was stirred in an ice bath for 12 h. After the stirring was completed, the mixture was purified to obtain product A.

[0095] S2: 9.24 g of 4-vinylbenzyl chloride and 19.01 g of triphenylphosphine were added sequentially to a container containing 115 mL of acetone, stirred for 10 min, and then evacuated and heated at 62°C for 48 h. After the reaction, the mixture was settled, washed, vacuum filtered, and dried to obtain product B.

[0096] S3: 4.23 g of product A, 0.095 g of product B and 13 mL of methanol were added to the container in sequence, and then 0.04 g of azobisisobutyronitrile was added, stirred for 10 min, vacuumed, heated at 65 ° C for 20 h, placed in a liquid nitrogen environment to quench the reaction, frozen, dialyzed, and vacuum dried to obtain product C; 0.027 g of product C, 0.033 g of divinylbenzene, 5.5 mL of methanol and 0.0045 g of azobisisobutyronitrile were added to the container in sequence, stirred for 10 min, vacuumed, heated at 70 ° C for 15 h, placed in liquid nitrogen to quench the reaction, settled, and purified to obtain a composite anti-fouling agent.

[0097] This embodiment discloses a method for preparing a soft light brick with a super anti-fouling coating, comprising the following steps:

[0098] Step 1: 48 g of kaolin, 26 g of quartz sand, 22 g of feldspar, 11 g of clay and 0.7 g of dispersant were mixed and wet ball milled. During the wet ball milling process, the ball-to-material ratio was 2:1, zirconia balls were used as the grinding medium, and the mixture was milled at 300-500 rpm for 6 h. The slurry fineness was controlled to be ≤5 μm. After the ball milling was completed, the mixture was allowed to stand at 25°C for 48 h to obtain a mixture.

[0099] Step 2: The mixture was pressed at 35 MPa for 120 seconds, dried by 2.45 GHz microwave, and sintered. The sintering process was as follows: heating from room temperature to 300°C at a heating rate of 3°C / min, holding for 45 minutes, then heating from 300°C to 1180°C at a heating rate of 5°C / min, holding for 90 minutes, and then naturally cooled to 200°C before being taken out of the furnace to obtain the matrix;

[0100] Step 3: Sandblast the substrate with 120-mesh corundum sand, with a compressed air pressure of 0.6 MPa and a spray distance of 25 cm. Then spray the hardener, followed by the composite anti-fouling agent, cure, and polish to obtain a soft light brick with a super anti-fouling coating.

[0101] Comparative Example 1: Compared with Example 1, in the process of preparing the soft light bricks in Comparative Example 1, no hardening agent is sprayed, and other conditions remain unchanged.

[0102] Comparative Example 2: Compared with Example 1, in the process of preparing the soft light bricks in Comparative Example 2, the composite anti-fouling agent is not sprayed, and other conditions remain unchanged.

[0103] Experimental Example: The soft light bricks prepared in Examples 1-5 and Comparative Examples 1-2 were tested. The performance of the samples was tested according to GB / T 4100-2015. The test results are shown in Table 1:

[0104] Table 1

[0105]

[0106] The test results in Table 1 show that the soft-light tiles prepared in Examples 1-5 of the present invention have excellent hardness, weather resistance, stain resistance, and wear resistance. A comparison between Comparative Example 1 and Examples 1-5 shows that spraying a hardener effectively improves their hardness, wear resistance, and weather resistance; a comparison between Comparative Example 2 and Examples 1-5 shows that spraying a composite anti-stain agent effectively improves their stain resistance and wear resistance.

[0107] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

[0108] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to specific embodiments. Obviously, many modifications and variations are possible based on the contents of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing a soft light brick with a super anti-fouling coating, characterized in that: The following steps are involved: Step 1: Mix kaolin, quartz sand, feldspar, clay and dispersant, and use wet ball milling. After the ball milling is completed, let it stand to obtain a mixture; Step 2: Pressing the mixture, drying it with microwaves, and sintering it to obtain a matrix; Step 3: sandblasting the substrate, spraying a hardening agent, and then spraying a composite antifouling agent, curing, and polishing to obtain a soft light brick with a super antifouling coating; The hardening agent is prepared from phosphorus oxychloride, 2,7-dimethoxynaphthalene, boron tribromide solution, diglycolic acid and pyrrolidine as main raw materials, and the composite antifouling agent is prepared from n-dodecyl mercaptan, carbon disulfide, methyl trioctyl ammonium chloride, 4-vinylbenzyl chloride, triphenylphosphine and divinylbenzene as main raw materials. The preparation method of the hardener comprises the following steps: Q1: In an ice bath, phosphorus oxychloride was added dropwise to N,N-dimethylformamide. After the addition was complete, the mixture was stirred at room temperature to obtain a mixed solution 1. 2,7-Dimethoxynaphthalene was then added to dichloromethane and stirred to dissolve to obtain a mixed solution 2. The mixed solution 1 was added dropwise to the mixed solution 2. After the addition was complete, the mixture was stirred at room temperature. The mixture was then added to deionized water, stirred, the pH was adjusted, extraction was performed, drying was performed, vacuum rotary evaporation was performed, recrystallization was performed, and vacuum drying was performed to obtain intermediate 1. The molecular structure of intermediate 1 is: ; Q2: Add intermediate 1 to dichloromethane, slowly add boron tribromide solution dropwise under nitrogen and ice bath, stir and react at room temperature after the addition is complete, add the product dropwise to a container filled with deionized water under ice bath, continue stirring and react at room temperature after the addition is complete, adjust the pH, extract, dry, evaporate under reduced pressure, and purify to obtain intermediate 2; The molecular structure of intermediate 2 is: ; Q3: Under a nitrogen atmosphere, diglycolic acid was added to the acid anhydride, heated with stirring to reflux, and phosphoric acid was added to catalyze the reaction. After the reaction, the product was evaporated under reduced pressure, concentrated, crystallized at low temperature, and filtered to obtain intermediate 3. Pyrrolidine was added to a container containing dichloromethane, followed by intermediate 3, and the reaction was stirred at room temperature. After the reaction, the product was evaporated under reduced pressure and crystallized at low temperature to obtain intermediate 4. The molecular structure of intermediate 3 is: The molecular structure of intermediate 4 is: ; Q4: Add intermediate 2 to N,N-dimethylformamide, add intermediate 4 under stirring, then dropwise add concentrated sulfuric acid, heat and stir to react, extract, adjust the pH, extract, dry, concentrate by distillation under reduced pressure, and purify to obtain a hardener; The molecular structure of the hardener is: ; The preparation method of the composite antifouling agent comprises the following steps: S1: n-Dodecanethiol, methyltrioctyl ammonium chloride, and acetone are added to a reaction vessel in sequence under an ice bath, followed by dropwise addition of sodium hydroxide solution and stirring, followed by addition of acetone and carbon disulfide, reaction, and then addition of chloroform and sodium hydroxide solution. After the addition is complete, stirring is carried out under ice bath, and purification is performed after the stirring is completed to obtain product A; S2: 4-vinylbenzyl chloride and triphenylphosphine are sequentially added to a container containing acetone, stirred, vacuumed, and then heated for reaction. After the reaction is completed, the mixture is settled, washed, vacuum filtered, and dried to obtain product B; S3: Add product A, product B and methanol to a container in sequence, then add azobisisobutyronitrile, stir, evacuate, heat to react, place in liquid nitrogen environment to quench the reaction, freeze, dialyze, and vacuum dry to obtain product C; add product C, divinylbenzene, methanol and azobisisobutyronitrile to a container in sequence, stir to react, evacuate, heat to react, place in liquid nitrogen to quench the reaction, settle, and purify to obtain a composite antifouling agent.

2. The method for preparing a soft light brick with a super anti-fouling coating according to claim 1, characterized in that: In the step 1, the dosage ratio of kaolin, quartz sand, feldspar, clay and dispersant is (40-50) g: (22-28) g: (18-23) g: (8-13) g: (0.4-0.8) g. During the wet ball milling process, the ball-to-material ratio is 2:1, zirconia balls are used as the grinding medium, and the mill is ground at 300-500 rpm for 4-6 hours. The slurry fineness is controlled to be ≤5 μm, and the mill is allowed to stand at 25° C. for 40-50 hours.

3. The method for preparing a soft light brick with a super anti-fouling coating according to claim 1, characterized in that: In the step 2, during the pressing process, the pressure is maintained at 30-35 MPa for 110-140 seconds, the microwave drying frequency is 2.45 GHz, and the sintering process is: heating from room temperature to 300°C at a heating rate of 3°C / min, keeping warm for 30-45 minutes, then heating from 300°C to 1180°C at a heating rate of 5°C / min, keeping warm for 80-100 minutes, and then naturally cooling to 200-220°C before being taken out of the furnace; in the step 3, during the sandblasting treatment, 120 mesh corundum sand is used, the compressed air pressure is 0.5-0.8 MPa, and the spray distance is 20-30 cm.

4. The method for preparing a soft light brick with a super anti-fouling coating according to claim 1, characterized in that: In the S1, the usage ratio of n-dodecanethiol, methyltrioctylammonium chloride, carbon disulfide and chloroform is (20.12-20.4) g: (0.98-1.05) g: (7.2-8.1) g: (17.12-18.74) g; in the S2, the usage ratio of 4-vinylbenzyl chloride, triphenylphosphine and acetone is (9.01-9.32) g: (18.45-19.12) g: (90-120) mL.

5. The method for preparing a soft light brick with a super anti-fouling coating according to claim 1, characterized in that: In S3, the usage ratio of product A, product B, methanol and azobisisobutyronitrile is (4.01-4.33) g: (0.08-0.1) g: (12-15) mL: (0.02-0.05) g; the usage ratio of product C, divinylbenzene, methanol and azobisisobutyronitrile is (0.01-0.032) g: (0.028-0.034) g: (4-6) mL: (0.002-0.005) g.

6. A soft light brick with a super anti-fouling coating prepared by the method according to any one of claims 1 to 5.

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