Colored enamel sintered sand liquid granite paint and preparation method thereof

Abstract

The present invention relates to the technical field of coating compositions, specifically disclosing a colored enamel sintered sand liquid granite coating and a preparation method thereof. The coating comprises the following components in parts by weight: 180-220 parts of water, 2-6 parts of a dispersant, 2-5 parts of a defoamer, 2-6 parts of a preservative, 7-14 parts of hydroxyethyl cellulose, 1-4 parts of a pH regulator, 2-8 parts of an antialgae agent, 5-12 parts of an antifreeze agent, 10-15 parts of a film-forming aid, 260-320 parts of a modified silicone acrylic emulsion, 8-12 parts of magnesium aluminum silicate, 4-8 parts of fumed silica, and 400-550 parts of colored enamel sintered sand. The present invention also provides a preparation method thereof. Compared with the prior art, the coating prepared by the present invention has the advantages of good weather resistance, high stability, and antibacterial and mildew resistance.

Description

Technical Field

[0001] The invention relates to the technical field of coating compositions, in particular to a colored enamel sintered sand liquid granite coating and a preparation method thereof. Background Art

[0002] With the rapid development of the economy and construction industry, imitation stone paint has gained widespread application in exterior decoration due to its ease of application, rich colors, and water-based, environmentally friendly properties. As imitation stone paint becomes more widespread in the construction industry, its variety is expanding, and its unique characteristics are becoming increasingly apparent. Water-based, multi-colored imitation stone paint for exterior walls is a coating that creates a decorative effect similar to that of natural stone. Made primarily from natural stone powders of varying colors and water-based, environmentally friendly materials, it achieves a natural color and excellent decorative effect. It is also waterproof and stain-resistant, effectively protecting buildings from the harsh external environment and extending their lifespan.

[0003] Chinese Patent No. 201710258801.1 relates to building materials and belongs to the technical field of wall-use architectural coatings. The present invention provides a new multi-colored imitation stone paint. Through the selection of raw materials and component optimization, particularly through the interaction between kaolin, modified cellulose, sodium salt dispersant, pure acrylic emulsion, and leveling agent, the product forms stable multi-colored imitation stone paint particles. Compared with the existing technology, there is a significant improvement in product storage stability, resulting in a new multi-colored imitation stone paint with good stability, good particle dispersibility, and no stratification, greatly expanding the transportation range and application range of the new multi-colored imitation stone paint. At the same time, the invention also provides a preparation method for the new multi-colored imitation stone paint. During the addition of modified cellulose, the addition rate is controlled to avoid agglomeration, which affects the performance of the multi-colored imitation stone paint particles.

[0004] Chinese Patent No. 201811510667.0 discloses an exterior stone-like paint composed of the following components: a base paint emulsion, coated aggregate, light-burned magnesium oxide, nano-silica sol, a siloxane coupling agent, lithium silicate, a pH adjuster, and additives. The coated aggregate comprises amorphous hollow vitrified microspheres coated with an 80-200 mesh natural colored sand adhesive layer and hard plastic regrind. The base paint emulsion is a self-crosslinking styrene-acrylic emulsion. The nano-silica sol has a pH of 7-9. The siloxane coupling agent is a vinyl-based siloxane coupling agent. The pH adjuster is an alcoholamine-based pH adjuster. The additives are two or more of a film-forming agent, a thickener, an antifreeze agent, a fungicide, and a defoamer. This exterior stone-like paint has a low specific gravity, a high specific heat capacity, is resistant to scouring, is not susceptible to stains, and exhibits excellent water resistance.

[0005] Because imitation stone paint has a poor application environment, especially when used on exterior walls, the light, temperature, and air environment are harsh, which can easily lead to paint film aging and denaturation. And because it is mostly used outdoors, it also faces the risk of mold and blackening. In the prior art, imitation stone paints mostly use physical addition methods to achieve antibacterial effects. Although this method is simple in process and has high sterilization efficiency, it has disadvantages such as easy sedimentation and easy migration of the antibacterial agent from the body, so it cannot achieve a long-term antibacterial effect. Therefore, it is necessary to provide an improved imitation stone paint and its preparation method to solve the problems existing in the prior art. Summary of the Invention

[0006] In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is a colored enamel sintered sand liquid granite paint and a preparation method thereof.

[0007] Adding antibacterial and mildew-proofing agents to coatings achieves its effect by slowly dispersing the fungicide into the environment. This effect is not only slow but also causes the coating to easily settle. The present invention successfully produces a structural antibacterial and mildew-proof coating by modifying a silicone-acrylic emulsion. Groups with antibacterial and mildew-proofing effects are introduced into the main body of the silicone-acrylic emulsion. After modification, the modified coating kills microorganisms through surface modification. Due to the strong chemical bond between the antibacterial groups and the main resin, the structural antibacterial coatings are not easily lost. Therefore, they can maintain long-term effective antimicrobial properties without polluting the environment. Furthermore, by modifying the siloxane used to prepare the silicone-acrylic emulsion, the hydrophobic groups present along with the monomers used in the silicone-acrylic emulsion modification also impart excellent stain resistance to the coating, thereby reducing the surface adhesion of microorganisms, preventing contaminants such as bacteria and viruses from binding to the surface, and making the surface easier to clean. Furthermore, the hydrogen phenanthrene ring introduced into the modified silicone not only has a surface energy-reducing effect, effectively reducing surface energy to achieve hydrophobicity, but also improves the mechanical properties of the coating due to its significant steric hindrance. Sintered sand has excellent weather resistance, outstanding adhesion, and outstanding chemical stability. Adding it to coatings not only improves stability but also greatly extends its service life.

[0008] To achieve the above object, the present invention provides a colored enamel sintered sand liquid granite paint, comprising the following components in parts by weight: 180-220 parts of water, 2-6 parts of a dispersant, 2-5 parts of a defoaming agent, 2-6 parts of a preservative, 7-14 parts of hydroxyethyl cellulose, 1-4 parts of a pH regulator, 2-8 parts of an antialgae agent, 5-12 parts of an antifreeze agent, 10-15 parts of a film-forming aid, 260-320 parts of a modified silicone acrylic emulsion, 8-12 parts of magnesium aluminum silicate, 4-8 parts of fumed silica, and 400-550 parts of colored enamel sintered sand.

[0009] The preparation method of the modified silicone acrylic emulsion comprises the following steps:

[0010] X1: Mix dimethylaminoethyl acrylate and decyl bromide, raise the temperature to 40-55°C, stir for 16-28 hours, cool to room temperature, filter, wash with n-hexane and acetone, and dry to obtain a monomer;

[0011] X2: (13S)-pimaran-8,16-diene-18-oic acid and O-benzotriazole-N,N,N',N'-tetramethyluronium tetrafluoroborate are added to N,N-dimethylformamide, followed by N,N-diisopropylethylamine. The mixture is stirred at room temperature for 1-2 hours, and then aminopropyltriethoxysilane is added. After stirring for 16-28 hours, the reaction solution is concentrated under reduced pressure to remove the solvent. The residue is diluted with dichloromethane and then washed with brine. After separation, the mixture is concentrated and dried to obtain a modified siloxane.

[0012] X3: Add methyl methacrylate, n-butyl acrylate, modified silicone, monomer, and hexadecyltrimethylammonium bromide to water, stir and mix evenly, then add hydrochloric acid to adjust the pH to 6-7, heat to 80-90°C under an inert atmosphere, add azobisisobutylammonium hydrochloride, stir evenly until the emulsion emits blue light, and keep warm for 10-30 minutes to obtain a seed emulsion; mix the monomer, hexadecyltrimethylammonium bromide, methyl methacrylate, n-butyl acrylate, and modified silicone, adjust the pH to 6-7 with hydrochloric acid, and stir for 2-4 hours to obtain a pre-emulsion; add azobisisobutylammonium hydrochloride to water and add it dropwise to the seed emulsion together with the pre-emulsion; after the addition is complete, keep warm for 2-4 hours, then cool to room temperature, and filter through a 100-200 mesh filter cloth to obtain a modified silicone acrylic emulsion.

[0013] Furthermore, the dispersant is an ammonium salt dispersant.

[0014] Furthermore, the defoaming agent is a silicone defoaming agent.

[0015] Furthermore, the preservative is 2-methyl-4-isothiazoline-3-one.

[0016] Furthermore, the pH regulator is aqueous ammonia.

[0017] Furthermore, the antialgae agent is one of chlorothalonil, 4,5-dichloro-N-octyl-4-isothiazoline-3-one or zinc pyrithione.

[0018] Furthermore, the antifreeze agent is one of ethylene glycol, glycerol or propylene glycol.

[0019] Furthermore, the film-forming aid is alcohol ester dodecanol.

[0020] Preferably, the preparation method of the modified silicone acrylic emulsion comprises the following steps:

[0021] X1: Mix 10-20 parts by weight of dimethylaminoethyl acrylate and 10-20 parts by weight of decyl bromide, raise the temperature to 40-55°C, stir for 16-28 hours, cool to room temperature, filter, wash with n-hexane and acetone, and dry to obtain a monomer;

[0022] X2: Add 2-4.5 parts by weight of (13S)-pimara-8,16-diene-18-oic acid and 3-5 parts by weight of O-benzotriazole-N,N,N',N'-tetramethyluronium tetrafluoroborate to 80-100 parts by weight of N,N-dimethylformamide, then add 2-4 parts by weight of N,N-diisopropylethylamine, and stir at room temperature for 1-2 hours. Then, add 2-5 parts by weight of aminopropyltriethoxysilane, and stir for 16-28 hours. Then, concentrate the reaction solution under reduced pressure to remove the solvent, dilute the residue with dichloromethane, wash with brine, separate the liquid, concentrate, and dry to obtain modified siloxane;

[0023] X3: Add 1-3 parts by weight of methyl methacrylate, 1-3 parts by weight of n-butyl acrylate, 0.1-0.5 parts by weight of modified silicone, 2-5 parts by weight of monomer, and 0.5-1 parts by weight of cetyltrimethylammonium bromide to 30-50 parts by weight of water, stir and mix evenly, then add hydrochloric acid to adjust the pH to 6-7, heat to 80-90°C under an inert atmosphere, add 0.04-0.1 parts by weight of azobisisobutylamidine hydrochloride, stir evenly until the emulsion turns blue, and keep warm for 10-30 minutes to obtain a seed emulsion; add 25-45 parts by weight of monomer; The invention discloses a method for preparing a modified silicone acrylic emulsion comprising mixing a pre-emulsion of 1,2-dimethyl-1,4-dimethyl-2-propenesulfonyl acrylate, ...

[0024] A method for preparing colored enamel sintered sand liquid granite coating comprises the following steps:

[0025] S1: Mix and grind the inorganic pigment and enamel glaze sintering aid, sieve, and then mix them evenly with quartz sand. Sinter at 350-900℃ for 10-15min to obtain colored enamel sintering sand.

[0026] S2: Mix water, preservative, dispersant and defoaming agent and stir evenly, continue to add hydroxyethyl cellulose, disperse evenly, add film-forming aid, antifreeze agent and modified silicone acrylic emulsion, mix evenly, add anti-algae agent, magnesium aluminum silicate, fumed silica and pH regulator, disperse evenly, add colored enamel sintered sand, stir evenly to obtain colored enamel sintered sand liquid granite coating.

[0027] Furthermore, the inorganic pigment powder is one of iron yellow, iron red or titanium dioxide.

[0028] Furthermore, the enamel glaze sintering aid is boron trioxide.

[0029] Preferably, the method for preparing the colored enamel sintered sand liquid granite coating comprises the following steps:

[0030] S1: 10-80 parts by weight of inorganic pigment and 10-20 parts of enamel glaze sintering aid are mixed and ground, then sieved, and then evenly mixed with 800-980 parts by weight of quartz sand. The mixture is sintered at 350-900°C for 10-15 minutes to obtain colored enamel sintered sand.

[0031] S2: Mix the formulated amount of water, preservatives, dispersants, and defoaming agents and stir them evenly, continue to add hydroxyethyl cellulose, disperse them evenly, add film-forming aids, antifreeze agents, and modified silicone acrylic emulsion, mix them evenly, add anti-algae agents, magnesium aluminum silicate, fumed silica, and pH regulator, disperse them evenly, add colored enamel sintered sand, and stir them evenly to obtain colored enamel sintered sand liquid granite coating.

[0032] Beneficial effects of the present invention:

[0033] 1. Compared with the prior art, the sintered sand prepared in the present invention has excellent weather resistance, outstanding adhesion, and outstanding chemical stability. Adding it to the coating not only improves the stability but also greatly extends the service life.

[0034] 2. Compared with the existing technology, the present invention modifies the silicone acrylic emulsion to give the coating antibacterial and mildew-proof properties, which not only reduces the risk of mildew and blackening, but also greatly extends the service life of the coating, enabling it to be used in more scenarios. DETAILED DESCRIPTION

[0035] (13S)-pimara-8,16-dien-18-oic acid, (13S)-pimara-8,16-dien-18-oic acid, CAS No.: 3625-01-2.

[0036] Defoaming agent, model: BYK-024, Buding Chemical.

[0037] Ammonium salt dispersant, model: Dispersant5029, Shandong Ruiyuan Biotechnology.

[0038] TEXANOL ester twelve, model: TEXANOL ester twelve, Guangzhou Ya Innovation Materials.

[0039] Silicone acrylic emulsion, product number: 31009, Gudao Chemical.

[0040] Hydrochloric acid, 6mol / L.

[0041] Ammonia, ≥25%, Aladdin.

[0042] Fumed silica, model: M-5, Shanghai Yizhu Industry.

[0043] Quartz sand, 60-160 mesh.

[0044] Escherichia coli, CGMCC1.2883, China General Microbiological Culture Collection Center.

[0045] Staphylococcus aureus, CGMCC1.282, China General Microbiological Culture Collection Center.

[0046] Comparative Example 1

[0047] A method for preparing colored enamel sintered sand liquid granite coating comprises the following steps:

[0048] S1: Mix 80g of titanium dioxide and 10g of boron trioxide, grind them together, pass through a 200-mesh sieve, and then mix them evenly with 900g of quartz sand. Sinter them at 800℃ for 10min to obtain colored enamel sintered sand.

[0049] S2: Mix 200mL of water, 2g of 2-methyl-4-isothiazoline-3-one, 96g of Dispersant 502, and 4g of BYK-024, stir evenly, continue to add 10g of hydroxyethyl cellulose, disperse evenly, add 10g of alcohol ester dodecahydrate, 8g of propylene glycol, and 300g of silicone acrylic emulsion, mix evenly, add 2g of 4,5-dichloro-N-octyl-4-isothiazoline-3-one, 10g of magnesium aluminum silicate, 5g of fumed silica, and 3g of ammonia water, disperse evenly, add 450g of colored enamel sintered sand, stir evenly, and obtain colored enamel sintered sand liquid granite coating.

[0050] Comparative Example 2

[0051] A method for preparing colored enamel sintered sand liquid granite coating comprises the following steps:

[0052] S1: Mix 80g of titanium dioxide and 10g of boron trioxide, grind them together, pass through a 200-mesh sieve, and then mix them evenly with 900g of quartz sand. Sinter them at 800℃ for 10min to obtain colored enamel sintered sand.

[0053] S2: Mix 200mL of water, 2g of 2-methyl-4-isothiazoline-3-one, 96g of Dispersant 502, and 4g of BYK-024, stir evenly, continue to add 10g of hydroxyethyl cellulose, disperse evenly, add 10g of alcohol ester twelve, 8g of propylene glycol and 300g of modified silicone acrylic emulsion, mix evenly, add 2g of 4,5-dichloro-N-octyl-4-isothiazoline-3-one, 10g of magnesium aluminum silicate, 5g of fumed silica, and 3g of ammonia water, disperse evenly, add 450g of colored enamel sintered sand, stir evenly to obtain colored enamel sintered sand liquid granite coating.

[0054] The preparation method of the modified silicone acrylic emulsion comprises the following steps:

[0055] X1: Mix 14 g of dimethylaminoethyl acrylate and 9.4 g of butyl bromide, heat to 50°C, and stir for 18 h. Cool to room temperature, filter, wash with n-hexane and acetone, and dry to obtain a monomer.

[0056] X2: 3 g of (13S)-pimaran-8,16-diene-18-oic acid and 3.5 g of O-benzotriazole-N,N,N',N'-tetramethyluronium tetrafluoroborate were added to 90 mL of N,N-dimethylformamide, followed by 3 g of N,N-diisopropylethylamine. The mixture was stirred at room temperature for 1 h, and then 3.5 g of aminopropyltriethoxysilane was added. After stirring for 24 h, the reaction solution was concentrated under reduced pressure to remove the solvent. The residue was diluted with dichloromethane and then washed with brine. After separation, the mixture was concentrated and dried to obtain a modified siloxane.

[0057] X3 Add 2g of methyl methacrylate, 1.5g of n-butyl acrylate, 0.3g of modified silicone, 3g of monomer, and 0.5g of cetyltrimethylammonium bromide to 45mL of water, stir and mix evenly, then add hydrochloric acid to adjust the pH to 6, heat to 85℃ under argon atmosphere, add 0.05g of azobisisobutylammonium hydrochloride, stir evenly until the emulsion turns blue, and keep warm for 30min to obtain a seed emulsion; mix 25g of monomer, 4.5g of cetyltrimethylammonium bromide, 45g of methyl methacrylate, 35g of n-butyl acrylate and 6g of modified silicone, adjust the pH to 6 with hydrochloric acid, and stir for 2h to obtain a pre-emulsion; add 0.5g of azobisisobutylammonium hydrochloride to 15mL of water and add it dropwise to the seed emulsion together with the pre-emulsion. After the addition is complete, keep warm at 85℃ for 3h, then cool to room temperature, and filter through a 200-mesh filter cloth to obtain a modified silicone acrylic emulsion.

[0058] Comparative Example 3

[0059] A method for preparing colored enamel sintered sand liquid granite coating comprises the following steps:

[0060] S1: Mix 80g of titanium dioxide and 10g of boron trioxide, grind them together, pass through a 200-mesh sieve, and then mix them evenly with 900g of quartz sand. Sinter them at 800℃ for 10min to obtain colored enamel sintered sand.

[0061] S2: Mix 200mL of water, 2g of 2-methyl-4-isothiazoline-3-one, 96g of Dispersant 502, and 4g of BYK-024, stir evenly, continue to add 10g of hydroxyethyl cellulose, disperse evenly, add 10g of alcohol ester twelve, 8g of propylene glycol and 300g of modified silicone acrylic emulsion, mix evenly, add 2g of 4,5-dichloro-N-octyl-4-isothiazoline-3-one, 10g of magnesium aluminum silicate, 5g of fumed silica, and 3g of ammonia water, disperse evenly, add 450g of colored enamel sintered sand, stir evenly to obtain colored enamel sintered sand liquid granite coating.

[0062] The preparation method of the modified silicone acrylic emulsion comprises the following steps:

[0063] X1: Mix 14 g of dimethylaminoethyl acrylate and 15 g of decyl bromide, heat to 50°C, and stir for 18 h. Cool to room temperature, filter, wash with n-hexane and acetone, and dry to obtain a monomer.

[0064] X2 Add 2g of methyl methacrylate, 1.5g of n-butyl acrylate, 0.3g of aminopropyltriethoxysilane, 3g of monomer, and 0.5g of hexadecyltrimethylammonium bromide to 45mL of water, stir and mix evenly, then add hydrochloric acid to adjust the pH to 6, heat to 85°C under argon atmosphere, add 0.05g of azobisisobutylammonium hydrochloride, stir evenly until the emulsion turns blue, and keep warm for 30min to obtain a seed emulsion; mix 25g of monomer, 4.5g of hexadecyltrimethylammonium bromide, 45g of methyl methacrylate, 35g of n-butyl acrylate, and 6g of aminopropyltriethoxysilane, adjust the pH to 6 with hydrochloric acid, and stir for 2h to obtain a pre-emulsion; add 0.5g of azobisisobutylammonium hydrochloride to 15mL of water and add it dropwise to the seed emulsion together with the pre-emulsion; after the addition is complete, keep warm at 85°C for 3h, then cool to room temperature, and filter through a 200-mesh filter cloth to obtain a modified silicone acrylic emulsion.

[0065] Example 1

[0066] A method for preparing colored enamel sintered sand liquid granite coating comprises the following steps:

[0067] S1: Mix 80g of titanium dioxide and 10g of boron trioxide, grind them together, pass through a 200-mesh sieve, and then mix them evenly with 900g of quartz sand. Sinter them at 800℃ for 10min to obtain colored enamel sintered sand.

[0068] S2: Mix 200mL of water, 2g of 2-methyl-4-isothiazoline-3-one, 96g of Dispersant 502, and 4g of BYK-024, stir evenly, continue to add 10g of hydroxyethyl cellulose, disperse evenly, add 10g of alcohol ester twelve, 8g of propylene glycol and 300g of modified silicone acrylic emulsion, mix evenly, add 2g of 4,5-dichloro-N-octyl-4-isothiazoline-3-one, 10g of magnesium aluminum silicate, 5g of fumed silica, and 3g of ammonia water, disperse evenly, add 450g of colored enamel sintered sand, stir evenly to obtain colored enamel sintered sand liquid granite coating.

[0069] The preparation method of the modified silicone acrylic emulsion comprises the following steps:

[0070] X1: Mix 14 g of dimethylaminoethyl acrylate and 15 g of decyl bromide, heat to 50°C, and stir for 18 h. Cool to room temperature, filter, wash with n-hexane and acetone, and dry to obtain a monomer.

[0071] X2: 3 g of (13S)-pimaran-8,16-diene-18-oic acid and 3.5 g of O-benzotriazole-N,N,N',N'-tetramethyluronium tetrafluoroborate were added to 90 mL of N,N-dimethylformamide, followed by 3 g of N,N-diisopropylethylamine. The mixture was stirred at room temperature for 1 h, and then 3.5 g of aminopropyltriethoxysilane was added. After stirring for 24 h, the reaction solution was concentrated under reduced pressure to remove the solvent. The residue was diluted with dichloromethane and then washed with brine. After separation, the mixture was concentrated and dried to obtain a modified siloxane.

[0072] X3 Add 2g of methyl methacrylate, 1.5g of n-butyl acrylate, 0.3g of modified silicone, 3g of monomer, and 0.5g of cetyltrimethylammonium bromide to 45mL of water, stir and mix evenly, then add hydrochloric acid to adjust the pH to 6, heat to 85℃ under argon atmosphere, add 0.05g of azobisisobutylammonium hydrochloride, stir evenly until the emulsion turns blue, and keep warm for 30min to obtain a seed emulsion; mix 25g of monomer, 4.5g of cetyltrimethylammonium bromide, 45g of methyl methacrylate, 35g of n-butyl acrylate and 6g of modified silicone, adjust the pH to 6 with hydrochloric acid, and stir for 2h to obtain a pre-emulsion; add 0.5g of azobisisobutylammonium hydrochloride to 15mL of water and add it dropwise to the seed emulsion together with the pre-emulsion; after the addition is complete, keep warm at 85℃ for 3h, then cool to room temperature, and filter through a 200-mesh filter cloth to obtain a modified silicone acrylic emulsion.

[0073] Example 2

[0074] The same as Example 1, the only difference being that the amount of hydroxyethyl cellulose is 12 g.

[0075] Example 3

[0076] The same as Example 1, the only difference being that the amount of hydroxyethyl cellulose is 14 g.

[0077] Example 4

[0078] The same as Example 1, the only difference is that the colored enamel sintered sand is 800g.

[0079] Example 5

[0080] The same as Example 1, the only difference is that the colored enamel sintered sand is 850g.

[0081] Test Example 1

[0082] The performance of colored enamel sintered sand liquid granite coatings was tested with reference to JG / T24-2018 "Synthetic Resin Emulsion Sand Wall Architectural Coatings". The limit values ​​were referenced to GB18582-2020 "Limits of Hazardous Substances in Architectural Wall Coatings". Specific data are shown in Table 1.

[0083] Table 1 Performance test results of colored enamel sintered sand liquid granite coating

[0084]

[0085]

[0086] Comparison of Control Example 1 with the Examples reveals that modification of the silicone acrylic emulsion successfully improved the coating's stability, water resistance, and stain resistance. Even after 15 days of heat storage, the coating remained free of mildew. This is due to the quaternary ammonium salt structure in the prepared monomer, which exhibits a good bactericidal effect. The modified silicone acrylic emulsion exhibits long-lasting, stable bactericidal and mildew-proof properties, and the resulting coating surface is less susceptible to microbial attachment, reducing the potential for contamination. Therefore, the Examples exhibited better performance than Control Example 1. However, Control Examples 2 and 3 differ from Example 1 in the monomers or siloxanes used, resulting in modified silicone acrylic emulsions with different hydrophobic groups and, consequently, different water resistance. The introduction of the hydrogen phenanthrene ring during siloxane modification in Example 1 not only affects hydrophobicity but also the mechanical properties of the coating. Compared with Examples 2-3, Example 1 uses a different amount of hydroxyethyl cellulose. As a hydrophilic thickener, hydroxyethyl cellulose is a hydrophilic material. As the amount of thickener added increases, the spatial network gaps formed within the emulsion become larger, causing the coating as a whole to easily absorb moisture, increasing its water vapor permeability and adhesion, which in turn leads to poor water permeability and stain resistance. Long-term influences from external environmental factors can also cause the surface of water-based multi-color coatings to yellow, fall off, or even crack. Compared with Example 1, Examples 4-5 use less colored enamel sintered sand. Since quartz sand has excellent properties for improving coating stability and adhesion, Example 1 exhibits better overall performance than Examples 4-5.

[0087] Test Example 2

[0088] The antibacterial and mildew-proofing tests were conducted on the colored enamel sintered sand liquid granite coatings prepared in the control example and the example according to the test method in GB / T 21866-2008, "Determination of Antibacterial Activity and Antibacterial Effect of Antibacterial Coatings (Paint Films)." The test strains included Escherichia coli and Staphylococcus aureus. Specific data are shown in Table 2.

[0089] Table 2 Antibacterial and mildew-proof test results of colored enamel sintered sand liquid granite coating

[0090]

[0091] From the antibacterial test, it can be seen that the antibacterial and mildew-proof effect of the coating layer was successfully improved by modifying the silicone acrylic emulsion in the embodiment. Not only did the long-term bactericidal effect achieve through the introduced antibacterial and mildew-proof groups, but also the hydrophobic groups introduced during the modification made it difficult for microorganisms to adhere to the surface. Therefore, not only was the antibacterial effect good, but the durability was also good. Compared with Example 1, Control Examples 2 to 3 lacked hydrophobic alkyl chains or hydrogen phenanthrene rings, so their stain resistance was poor, which affected their antibacterial properties. Examples 2 to 5 were not much different from Example 1. By modifying the silicone acrylic emulsion to give the coating antibacterial and mildew-proof properties, not only can the risk of mold and blackening be reduced, but the service life of the coating can also be greatly extended, allowing it to be used in more scenarios.

[0092] The above describes in detail the preferred embodiments of the present invention. It should be understood that those skilled in the art can make numerous modifications and variations based on the concepts of the present invention without inventive effort. Therefore, any technical solutions that can be derived by those skilled in the art through logical analysis, reasoning, or limited experimentation based on the concepts of the present invention and the prior art should be within the scope of protection defined by the claims.

Claims

1. A colored enamel sintered sand liquid granite paint, characterized in that, The invention comprises the following components in parts by weight: 180-220 parts of water, 2-6 parts of dispersant, 2-5 parts of defoaming agent, 2-6 parts of preservative, 7-14 parts of hydroxyethyl cellulose, 1-4 parts of pH regulator, 2-8 parts of antialgae agent, 5-12 parts of antifreeze agent, 10-15 parts of film-forming aid, 260-320 parts of modified silicone acrylic emulsion, 8-12 parts of magnesium aluminum silicate, 4-8 parts of fumed silica and 400-550 parts of colored enamel sintered sand; The preparation method of the modified silicone acrylic emulsion comprises the following steps: X1: Mix 10-20 parts by weight of dimethylaminoethyl acrylate and 10-20 parts by weight of decyl bromide, raise the temperature to 40-55°C, stir for 16-28 hours, cool to room temperature, filter, wash with n-hexane and acetone, and dry to obtain a monomer; X2: Add 2-4.5 parts by weight of (13S)-pimara-8,16-diene-18-oic acid and 3-5 parts by weight of O-benzotriazole-N,N,N',N'-tetramethyluronium tetrafluoroborate to 80-100 parts by weight of N,N-dimethylformamide, then add 2-4 parts by weight of N,N-diisopropylethylamine, and stir at room temperature for 1-2 hours. Then, add 2-5 parts by weight of aminopropyltriethoxysilane, and stir for 16-28 hours. Then, concentrate the reaction solution under reduced pressure to remove the solvent, dilute the residue with dichloromethane, wash with brine, separate the liquid, concentrate, and dry to obtain the modified siloxane; X3: Add 1-3 parts by weight of methyl methacrylate, 1-3 parts by weight of n-butyl acrylate, 0.1-0.5 parts by weight of modified silicone, 2-5 parts by weight of monomer, and 0.5-1 parts by weight of cetyltrimethylammonium bromide to 30-50 parts by weight of water, stir and mix evenly, then add hydrochloric acid to adjust the pH to 6-7, heat to 80-90°C under an inert atmosphere, add 0.04-0.1 parts by weight of azobisisobutylamidine hydrochloride, stir evenly until the emulsion turns blue, and keep warm for 10-30 minutes to obtain a seed emulsion; add 25-45 parts by weight of monomer; The invention discloses a method for preparing a modified silicone acrylic emulsion comprising mixing a pre-emulsion of 1,2-dimethyl-1,4-dimethyl-2-propenesulfonyl acrylate, ...

2. The colored enamel sintered sand liquid granite paint according to claim 1, characterized in that: The dispersant is an ammonium salt dispersant.

3. The colored enamel sintered sand liquid granite paint according to claim 1, characterized in that: The defoaming agent is an organosilicon defoaming agent.

4. The colored enamel sintered sand liquid granite paint according to claim 1, characterized in that: The preservative is 2-methyl-4-isothiazoline-3-one.

5. The colored enamel sintered sand liquid granite paint according to claim 1, characterized in that: The pH regulator is aqueous ammonia.

6. The colored enamel sintered sand liquid granite paint according to claim 1, characterized in that: The antialgae agent is one of chlorothalonil, 4,5-dichloro-N-octyl-4-isothiazoline-3-one or zinc pyrithione.

7. The colored enamel sintered sand liquid granite paint according to claim 1, characterized in that: The antifreeze agent is one of ethylene glycol, glycerol or propylene glycol.

8. The colored enamel sintered sand liquid granite paint according to claim 1, characterized in that: The film-forming aid is alcohol ester dodecanol.

9. A method for preparing the colored enamel sintered sand liquid granite paint according to any one of claims 1 to 8, characterized in that: The steps include: S1: Mix and grind the inorganic pigment and enamel glaze sintering aid, sieve, and then mix them evenly with quartz sand. Sinter at 350-900℃ for 10-15min to obtain colored enamel sintering sand. S2: Mix water, preservative, dispersant and defoaming agent and stir evenly, continue to add hydroxyethyl cellulose, disperse evenly, add film-forming aid, antifreeze agent and modified silicone acrylic emulsion, mix evenly, add anti-algae agent, magnesium aluminum silicate, fumed silica and pH regulator, disperse evenly, add colored enamel sintered sand, stir evenly to obtain colored enamel sintered sand liquid granite coating.

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