A high-hardness glaze coating and its preparation method

Abstract

The present invention belongs to the technical field of coating preparation, and specifically relates to a high-hardness glazed coating and a preparation method thereof. In terms of mass percentage, the high-hardness glazed coating is prepared from the following raw materials: 20-30% fluorinated silicon propylene emulsion, 5-20% potassium silicate solution, 8-35% composite filler, 2-8% functional auxiliary, 2-6% film-forming auxiliary, and 20-60% water; wherein, the composite filler is prepared from titanium dioxide, silicon dioxide, bentonite and attapulgite as raw materials. The glazed coating prepared by the present invention has high hardness, crack resistance, water resistance and good weather resistance, and excellent comprehensive performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of coating preparation, and particularly relates to a high-hardness glazed coating and a preparation method thereof. Background Art

[0002] With the improvement of people's living standards, different types of wall coatings have been developed and used. As a new type of building coating with excellent performance, the glazed coating has the same texture as the tile glaze, is easy to clean, and has a wide range of applications in the fields of woodware, anti-corrosion, etc. Common glazed paints include water-based glazed paints and solvent-based glazed paints. Among them, the solvent-based glazed paint has been gradually abandoned by the market due to the complexity of its process and large pollution, while the water-based glazed paint has gradually occupied the mainstream of the market.

[0003] In the prior art, for example, Chinese patent document CN110922795A provides an exterior wall inorganic glazed coating and a preparation method thereof, including the following raw materials in parts by weight: sericite powder 20-25 parts, quartz powder 20-25 parts, white cement 15-20 parts, ore powder 10-15 parts, zeolite powder 10-15 parts, hydrated lime powder 5-10 parts, heavy calcium powder 5-10 parts, white carbon black 1-2 parts, nano-silica 1-2 parts, nano-magnesium oxide 1-2 parts, hydrophobic rubber powder 2-5 parts, water repellent 0.5-1 part, cellulose 0.5-1 part, alkali inhibitor 0.3-0.5 part; the provided exterior wall inorganic glazed coating uses the polymerization reaction between mineral materials to form a geopolymers, which is used as the cementing material for the exterior wall coating. Spraying a small amount of the above exterior wall inorganic glazed coating can make it integrate with the wall. However, it can be seen that the above glazed coating completely relies on organic materials to bond to the wall, and while the adhesion needs to be further improved, the hardness is also average, and the overall performance needs to be improved.

[0004] Chinese Patent Document CN112795215A provides a sand-containing glaze coating, its preparation method and application, which are prepared from the following raw materials in parts by weight: 10-20 parts of emulsion, 10-30 parts of natural sand, 5-30 parts of light calcium, 20-50 parts of filler, 0.4-1 part, 12-25 parts of water, 0.1-0.6 part of dispersant, 0.1-0.6 part of wetting agent, 0.2-0.6 part of defoaming agent, 0.2-2.0 parts of film-forming aid, 0.5-5 parts of titanium dioxide, 0.1-0.4 part of pH regulator, 0.1-2.0 parts of antifreeze, 0.1-0.6 part of preservative. Its formula includes specific parts by weight of emulsion, natural sand, specific light calcium, filler and water. The natural sand is firmly wrapped in the mixture of emulsion, filler and light calcium, improving the flatness, reducing the rough feel of the natural sand, and not covering the natural color of the natural sand, making it meet the stone imitation effect. And the addition of solid materials can also ensure the hardness and wear resistance of the real stone paint and reduce the cost. The formed paint film has the characteristics of strong glaze effect, good adhesion, corrosion resistance, smooth surface, full sense, scrub resistance, moisture resistance, mildew resistance and excellent mechanical properties. However, it can be seen that the filler used is directly added, which greatly affects the dispersion of the filler in the emulsion.

[0005] Based on this, the present invention hopes to provide an environmentally friendly glaze coating with high hardness and excellent comprehensive performance. Summary of the Invention

[0006] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide a high-hardness glaze coating and its preparation method, which has high hardness, anti-cracking, water resistance, good weather resistance and excellent comprehensive performance.

[0007] To achieve the above purpose, the present invention adopts the following technical solutions:

[0008] In the first aspect, the present invention provides a high-hardness glaze coating, which is prepared from the following raw materials in mass percentage:

[0009] 20-30% fluorinated silicon propyl emulsion, 5-20% potassium silicate solution, 8-35% composite filler, 2-8% functional auxiliary, 2-6% film-forming auxiliary, 20-60% water;

[0010] Among them, the composite filler is prepared from titanium dioxide, silicon dioxide, bentonite and attapulgite as raw materials.

[0011] Preferably, the preparation of the composite filler includes the following steps:

[0012] S1. Mix bentonite and attapulgite, first perform crushing and sieving treatment, and then treat with hydrochloric acid solution. After the treatment is completed, perform filtration, washing and drying treatment to obtain Material I;

[0013] S2. Mix the material I obtained in step S1 with sodium hydroxide evenly and then conduct high-temperature treatment. After the treatment is completed, obtain material II;

[0014] S3. Add the material II obtained in step S2 into an aqueous solution containing dodecylmethyldihydroxyethylammonium bromide, and then conduct treatment under heating conditions. After the treatment is completed, first perform centrifugation, washing, and drying, and finally conduct activation; after the activation is completed, obtain material III;

[0015] S4. Add silica to a solvent, disperse evenly, then add succinic anhydride and KH550, maintain centrifugal stirring and conduct heating treatment. After the treatment is completed, perform centrifugation, washing, and drying to obtain material IV;

[0016] S5. Add titanium dioxide, the material III obtained in step S3, and the material IV obtained in step S4 into water, and conduct stirring treatment under heating conditions. After the treatment is completed, perform suction filtration, drying, and grinding to obtain the composite filler.

[0017] Further preferably, in step S1, the mass ratio of bentonite to attapulgite is 1:1.5 - 2.5, and it is sieved through 80 - 150 meshes; the concentration of the hydrochloric acid solution is 10 - 15 wt%, the temperature for the hydrochloric acid solution treatment is room temperature, and the treatment time is 2 - 6 h.

[0018] Further preferably, in step S2, the mass ratio of material I to sodium hydroxide is 1:0.3 - 0.65, the high-temperature treatment temperature is 710 - 780 °C, and the treatment time is 0.5 - 2 h.

[0019] Further preferably, in step S3, the concentration of dodecylmethyldihydroxyethylammonium bromide is 4 - 8 wt%, the mass ratio of material II to dodecylmethyldihydroxyethylammonium bromide is 1:0.3 - 0.6; the heating treatment temperature is 50 - 70 °C, and the treatment time is 1 - 6 h; the activation treatment temperature is 100 - 110 °C, and the activation time is 0.5 - 4 h.

[0020] Further preferably, in step S4, the solvent is DMF, and the mass ratio of silica, solvent, succinic anhydride, and KH550 is 1:50 - 70:2 - 3.5:5 - 8; the centrifugal stirring rate is 80 - 150 rpm; the heating treatment temperature is 30 - 40 °C, and the treatment time is 1 - 6 h.

[0021] Further preferably, in step S5, the mass ratio of titanium dioxide, material III, and material IV is 1:0.4 - 0.7:0.5 - 0.9; the heating treatment temperature is 25 - 35 °C, and the treatment time is 1 - 4 h.

[0022] Preferably, the functional additives are selected from one or more of a dispersant, an antifoaming agent, an antifreezing agent, a wetting agent, a pH regulator, a preservative, a mildew preventive, a leveling agent, and a thickener.

[0023] Preferably, the film-forming aids are selected from one or more of propylene glycol, ethylene glycol, and alcohol ester-based film-forming aids.

[0024] In a second aspect, the present invention provides a method for preparing the above high-hardness glaze coating, which is characterized by comprising the following steps:

[0025] Mix half of the mass of water, the fluorosilicone propylene emulsion, the potassium silicate solution, the functional additives, and the film-forming aids, stir evenly, and then add the composite filler and the other half of the mass of water, and stir evenly again to obtain the product.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] The glaze coating provided by the present invention uses the fluorosilicone propylene emulsion and the potassium silicate solution as the main film-forming substances, and selects the composite filler and related additives to improve the film-forming properties, so that the prepared coating has the effects of high hardness, crack resistance, water resistance, etc., and has good comprehensive performance.

[0028] The glaze coating provided by the present invention uses a specific composite filler, which is prepared from titanium dioxide, silicon dioxide, bentonite and attapulgite. Among them, titanium dioxide has excellent whiteness and covering power, and can effectively improve the smoothness and covering ability of the coating. However, it has the deficiencies of poor weather resistance and easy agglomeration. Therefore, in the present invention, while retaining the use of titanium dioxide, the use of silicon dioxide, bentonite and attapulgite is used to reduce its dosage and improve the deficiencies brought by its use; quartz powder is often used in traditional glaze coatings. Although it can improve the hardness of the glaze coating, its density is relatively large, and the use of a large amount will increase the overall weight of the coating and increase the spraying difficulty. Therefore, in the present invention, a small amount of silicon dioxide is used to replace it. While controlling the use, it can greatly improve the hardness of the glaze coating and improve the weather resistance. The use of silicon dioxide itself has the problem of easy agglomeration. Therefore, in the present invention, it is modified with acid anhydride to introduce carboxyl groups. On the one hand, it reduces the agglomeration tendency, and on the other hand, the introduced amino groups can be efficiently compounded with the hydroxyl groups contained in the modified bentonite and attapulgite; in addition, the use of silicon dioxide will also correspondingly increase the brittleness of the glaze coating system. Therefore, in the present invention, a clay composite mainly composed of attapulgite and bentonite is introduced, which is beneficial to improving the toughness and impact resistance of the glaze coating. During the use process, the present invention makes corresponding treatments on attapulgite and bentonite. Specifically, in the present invention, the composite of bentonite and attapulgite is first pickled, which is beneficial to removing impurities and preliminarily improving the pore structure of the clay and improving the activity. Then, the acid-treated material I is subjected to high-temperature alkali treatment, which is beneficial to improving the thermal stability and pore structure of bentonite and attapulgite, promoting the stability of the system and improving its activity. Finally, the obtained material II is treated with dodecylmethyldihydroxyethylammonium bromide. On the one hand, it is hoped to further reduce the agglomeration of the clay, and on the other hand, based on the introduced hydroxyl groups, a hydrogen bond system is formed with the modified silicon dioxide and fluorosilicone propylene emulsion, ensuring the compactness of the composite filler filled in the emulsion, improving the film-forming quality, and further improving the properties of the glaze coating.

[0029] When the present invention uses bentonite and attapulgite, the two are treated simultaneously, which simplifies the treatment process; in addition, for the dosages of bentonite and attapulgite, in the present invention, the ratio is preferably controlled at 1:1.5 - 2.5 to ensure good rheological properties and adhesion, and synergistically improve the comprehensive performance of the glaze coating.

[0030] In short, the present invention ensures the hardness, wear resistance, weather resistance and other properties of the prepared glaze coating through the selection of components and specific modifications, and has good comprehensive performance. Detailed Embodiments

[0031] The embodiments of the present invention are described in detail below. All embodiments are exemplary and are intended to explain the present invention and should not be construed as a limitation of the present invention.

[0032] In the present invention, the potassium silicate solution has the model number DY-28 and is purchased from Xingtai Dayang Chemical Co., Ltd.; the fluorinated silicon propyl emulsion is prepared with reference to the prior art, such as being prepared according to Example 1 of Patent Document CN118440552A, or being prepared according to Example 1 of Patent Document CN106632876A. Preferably, it is prepared with reference to CN106632876A.

[0033] In the examples of the present invention, the film-forming aid is selected as an alcohol ester film-forming aid, preferably with the brand name OE300, and is purchased from Shanghai Jiushi Chemical Co., Ltd.

[0034] In the examples of the present invention, attapulgite is purchased from Sishui Yuexin Foundry Materials Factory; the dispersant has the brand name BYK110; the defoamer has the brand name BYK067; the wetting agent is an organosilicon defoamer with the brand name TEGO AIREX 902W; the leveling agent has the brand name BYK377.

[0035] In the examples of the present invention, the silica has the brand name Degussa A380 and is purchased from Degussa Chemical Co., Ltd.; bentonite is purchased from Wuhu Shuohua New Material Technology Co., Ltd.

[0036] For other raw materials not specified, they are all purchased from the market and are generally available to those skilled in the art.

[0037] Example 1

[0038] A high-hardness glaze coating is prepared from the following raw materials based on 100% by mass percentage: 22% fluorinated silicon propyl emulsion, 13% potassium silicate solution, 32% composite filler, 0.5% dispersant, 0.4% defoamer, 0.6% leveling agent, 0.6% wetting agent, 3% film-forming aid, and the balance is water.

[0039] Among them, the preparation of the composite filler includes the following steps:

[0040] S1. Mix bentonite and attapulgite in a mass ratio of 1:2, first crush and sieve them through 100 meshes, and then treat them with a 12 wt% hydrochloric acid solution (room temperature, 4 h). After the treatment is completed, filter, wash, and dry to obtain Material I.

[0041] S2. Mix the Material I obtained in step S1 and sodium hydroxide in a mass ratio of 1:0.45, mix them evenly, and then perform high-temperature treatment (720 °C, 0.5 h). After the treatment is completed, obtain Material II.

[0042] S3. Add the obtained Material II from Step S2 into an aqueous solution (4.5 wt%) containing dodecylmethyldihydroxyethylammonium bromide, and then conduct treatment under heating conditions (68 °C, 3.5 h). After the treatment is completed, first perform centrifugation, washing, and drying, and finally conduct activation (102 °C, 1 h); after the activation is completed, obtain Material III; wherein, the mass ratio of Material II to dodecylmethyldihydroxyethylammonium bromide is 1:0.35;

[0043] S4. Add silica into N,N-dimethylformamide (DMF), and after dispersing evenly, add succinic anhydride and KH550, maintain centrifugal stirring and conduct heating treatment (35 °C, 2 h). After the treatment is completed, conduct centrifugation (100 rpm), washing, and drying to obtain Material IV; wherein, the mass ratio of silica, solvent, succinic anhydride, and KH550 is 1:60:2.8:6.5;

[0044] S5. Add titanium dioxide, the obtained Material III from Step S3, and the obtained Material IV from Step S4 into water according to the mass ratio of 1:0.5:0.65, and conduct stirring treatment under heating conditions (30 °C, 2 h). After the treatment is completed, conduct suction filtration, drying, and grinding to obtain the composite filler.

[0045] In this embodiment, a preparation method of the above high-hardness glaze coating is also provided, including the following steps:

[0046] Mix half of the mass of water, fluorosilicone propylene emulsion, potassium silicate solution, functional auxiliaries (dispersant, defoamer, leveling agent, wetting agent), and film-forming auxiliary and stir evenly, and then add the composite filler and the other half of the mass of water, and stir evenly again to obtain the product.

[0047] Example 2

[0048] A high-hardness glaze coating is prepared from the following raw materials by mass percentage of 100%: 23% fluorosilicone propylene emulsion, 12% potassium silicate solution, 35% composite filler, 0.5% dispersant, 0.4% defoamer, 0.6% leveling agent, 0.6% wetting agent, 3% film-forming auxiliary, and the balance is water.

[0049] Among them, the preparation of the composite filler includes the following steps:

[0050] S1. Mix bentonite and attapulgite according to the mass ratio of 1:2.2, first conduct crushing and sieving through a 100-mesh sieve, and then conduct treatment with a 13 wt% hydrochloric acid solution (room temperature, 4 h). After the treatment is completed, conduct filtration, washing, and drying to obtain Material I;

[0051] S2. Mix the material Ⅰ obtained in step S1 with sodium hydroxide in a mass ratio of 1:0.5, and then conduct high-temperature treatment (715 °C, 40 min). After the treatment is completed, obtain material Ⅱ.

[0052] S3. Add the material Ⅱ obtained in step S2 into an aqueous solution containing dodecyl methyldihydroxyethyl ammonium bromide (4.8 wt%), and then conduct treatment under heating conditions (65 °C, 3 h). After the treatment is completed, first perform centrifugation, washing, and drying, and finally conduct activation (105 °C, 1 h); after the activation is completed, obtain material Ⅲ; wherein, the mass ratio of the material Ⅱ to dodecyl methyldihydroxyethyl ammonium bromide is 1:0.35.

[0053] S4. Add silica into N,N-dimethylformamide (DMF), disperse evenly, then add succinic anhydride and KH550, maintain centrifugal stirring and conduct heating treatment (35 °C, 1.5 h). After the treatment is completed, conduct centrifugation (100 rpm), washing, and drying to obtain material Ⅳ; wherein, the mass ratio of silica, solvent, succinic anhydride, and KH550 is 1:65:2.6:6.7.

[0054] S5. Add titanium dioxide, the material Ⅲ obtained in step S3, and the material Ⅳ obtained in step S4 into water in a mass ratio of 1:0.45:0.68, and conduct stirring treatment under heating conditions (30 °C, 2 h). After the treatment is completed, conduct suction filtration, drying, and grinding to obtain the composite filler.

[0055] In this embodiment, a preparation method of the above high-hardness glaze coating is also provided, including the following steps:

[0056] Mix half of the mass of water, fluorosilicone propylene emulsion, potassium silicate solution, functional auxiliaries (dispersant, defoamer, leveling agent, wetting agent), and film-forming auxiliaries, stir evenly, then add the composite filler and the other half of the mass of water, and stir evenly again.

[0057] Example 3

[0058] A high-hardness glaze coating is prepared from the following raw materials by mass percentage of 100%: 21% fluorosilicone propylene emulsion, 14% potassium silicate solution, 33% composite filler, 0.5% dispersant, 0.4% defoamer, 0.6% leveling agent, 0.6% wetting agent, 3% film-forming auxiliary, and the balance is water.

[0059] Among them, the preparation of the composite filler includes the following steps:

[0060] S1. Mix bentonite and attapulgite in a mass ratio of 1:2.2, first crush and sieve them through 100 meshes, and then treat them with 12 wt% hydrochloric acid solution (room temperature, 4 h). After the treatment is completed, filter, wash, and dry to obtain Material I;

[0061] S2. Mix the Material I obtained in step S1 and sodium hydroxide in a mass ratio of 1:0.48, and then perform high-temperature treatment (725 °C, 0.5 h). After the treatment is completed, obtain Material II;

[0062] S3. Add the Material II obtained in step S2 into an aqueous solution containing dodecyl methyldihydroxyethyl ammonium bromide (4.2 wt%), and then perform treatment under heating conditions (68 °C, 3.5 h). After the treatment is completed, first centrifuge, wash, and dry, and finally activate (104 °C, 1 h); after the activation is completed, obtain Material III; wherein, the mass ratio of Material II to dodecyl methyldihydroxyethyl ammonium bromide is 1:0.38;

[0063] S4. Add silicon dioxide into N,N-dimethylformamide (DMF), disperse it evenly, then add succinic anhydride and KH550, maintain centrifugal stirring and perform heating treatment (35 °C, 2 h). After the treatment is completed, centrifuge (100 rpm), wash, and dry to obtain Material IV; wherein, the mass ratio of silicon dioxide, solvent, succinic anhydride, and KH550 is 1:60:2.9:6.3;

[0064] S5. Add titanium dioxide, the Material III obtained in step S3, and the Material IV obtained in step S4 into water in a mass ratio of 1:0.55:0.6, and perform stirring treatment under heating conditions (30 °C, 2 h). After the treatment is completed, perform suction filtration, drying, and grinding to obtain the composite filler.

[0065] In this example, a preparation method of the above high-hardness glaze coating is also provided, including the following steps:

[0066] Mix half of the mass of water, fluorosilicon propylene emulsion, potassium silicate solution, functional auxiliaries (dispersant, defoamer, leveling agent, wetting agent), and film-forming auxiliaries, stir evenly, then add the composite filler and the other half of the mass of water, and stir evenly again.

[0067] Comparative Example 1

[0068] Compared with Example 1, in Comparative Example 1, all bentonite was used, that is, attapulgite was also replaced with bentonite, and the others were the same. Specifically, in this comparative example, a high-hardness glaze coating was provided, which was prepared from the following raw materials based on 100% by mass percentage: 22% fluorinated silicon propylene emulsion, 13% potassium silicate solution, 32% composite filler, 0.5% dispersant, 0.4% defoamer, 0.6% leveling agent, 0.6% wetting agent, 3% film-forming aid, and the balance was water.

[0069] Among them, the preparation of the composite filler includes the following steps:

[0070] S1. First, the bentonite was crushed and screened through 100 meshes, and then treated with a 12 wt% hydrochloric acid solution (room temperature, 4 h). After the treatment was completed, it was filtered, washed, and dried to obtain Material I;

[0071] S2. The Material I obtained in step S1 was mixed with sodium hydroxide in a mass ratio of 1:0.45 and then subjected to high-temperature treatment (720 °C, 0.5 h). After the treatment was completed, Material II was obtained;

[0072] S3. The Material II obtained in step S2 was added to an aqueous solution containing dodecyl methyl dihydroxyethyl ammonium bromide (4.5 wt%), and then treated under heating conditions (68 °C, 3.5 h). After the treatment was completed, it was first centrifuged, washed, and dried, and finally activated (102 °C, 1 h); after the activation was completed, Material III was obtained; among them, the mass ratio of Material II to dodecyl methyl dihydroxyethyl ammonium bromide was 1:0.35;

[0073] S4. Silicon dioxide was added to N,N-dimethylformamide (DMF), and after being dispersed evenly, succinic anhydride and KH550 were added, and centrifugal stirring was maintained and heating treatment was carried out (35 °C, 2 h). After the treatment was completed, it was centrifuged (100 rpm), washed, and dried to obtain Material IV; among them, the mass ratio of silicon dioxide, solvent, succinic anhydride, and KH550 was 1:60:2.8:6.5;

[0074] S5. Titanium dioxide, the Material III obtained in step S3, and the Material IV obtained in step S4 were added to water in a mass ratio of 1:0.5:0.65, and stirred under heating conditions (30 °C, 2 h). After the treatment was completed, it was suction-filtered, dried, and ground to obtain the composite filler.

[0075] In this comparative example, a preparation method of the above high-hardness glaze coating was also provided, including the following steps:

[0076] Mix half of the mass of water, fluorinated silicon propyl emulsion, potassium silicate solution, functional additives (dispersant, defoamer, leveling agent, wetting agent), and film-forming aid evenly by stirring, and then add composite filler and the other half of the mass of water, and stir evenly again to obtain the product.

[0077] Comparative Example 2

[0078] Compared with Example 1, in Comparative Example 2, all attapulgite is used, that is, bentonite is replaced by attapulgite, and others are the same. Specifically, in this comparative example, a high-hardness glazed coating is provided, and calculated by 100% by mass percentage, it is prepared from the following raw materials: 22% fluorinated silicon propyl emulsion, 13% potassium silicate solution, 32% composite filler, 0.5% dispersant, 0.4% defoamer, 0.6% leveling agent, 0.6% wetting agent, 3% film-forming aid, and the balance is water.

[0079] Among them, the preparation of the composite filler includes the following steps:

[0080] S1. First, crush and sieve attapulgite through 100 meshes, and then treat it with 12wt% hydrochloric acid solution (room temperature, 4h). After the treatment is completed, filter, wash, and dry to obtain Material I;

[0081] S2. Mix the Material I obtained in step S1 with sodium hydroxide in a mass ratio of 1:0.45 evenly and then carry out high-temperature treatment (720°C, 0.5h). After the treatment is completed, obtain Material II;

[0082] S3. Add the Material II obtained in step S2 into an aqueous solution containing dodecyl methyl dihydroxyethyl ammonium bromide (4.5wt%), and then carry out treatment under heating conditions (68°C, 3.5h). After the treatment is completed, first carry out centrifugation, washing, and drying, and finally carry out activation (102°C, 1h); after the activation is completed, obtain Material III; among them, the mass ratio of Material II to dodecyl methyl dihydroxyethyl ammonium bromide is 1:0.35;

[0083] S4. Add silicon dioxide into N,N-dimethylformamide (DMF), disperse evenly, then add succinic anhydride and KH550, keep centrifugal stirring and carry out heating treatment (35°C, 2h). After the treatment is completed, carry out centrifugation (100rpm), washing, and drying to obtain Material IV; among them, the mass ratio of silicon dioxide, solvent, succinic anhydride, and KH550 is 1:60:2.8:6.5;

[0084] S5. Add titanium dioxide, the Material III obtained in step S3, and the Material IV obtained in step S4 into water in a mass ratio of 1:0.5:0.65, and carry out stirring treatment under heating conditions (30°C, 2h). After the treatment is completed, carry out suction filtration, drying, and grinding to obtain the composite filler.

[0085] In this comparative example, a preparation method of the above high-hardness glaze coating is also provided, including the following steps:

[0086] Mix half of the mass of water, fluorosilicone propylene emulsion, potassium silicate solution, functional additives (dispersant, defoamer, leveling agent, wetting agent), and film-forming aid evenly by stirring, and then add composite filler and the other half of the mass of water, and stir evenly again to obtain the product.

[0087] Comparative Example 3

[0088] Compared with Example 1, in Comparative Example 2, high-temperature treatment is not carried out, that is, step S2 is omitted, and the rest are the same. Specifically, in this comparative example, a high-hardness glaze coating is provided. Calculated based on 100% by mass percentage, it is prepared from the following raw materials: 22% fluorosilicone propylene emulsion, 13% potassium silicate solution, 32% composite filler, 0.5% dispersant, 0.4% defoamer, 0.6% leveling agent, 0.6% wetting agent, 3% film-forming aid, and the balance is water.

[0089] Among them, the preparation of the composite filler includes the following steps:

[0090] S1. Mix bentonite and attapulgite in a mass ratio of 1:2, first crush and sieve them through a 100-mesh sieve, and then treat them with a 12 wt% hydrochloric acid solution (room temperature, 4 h). After the treatment is completed, filter, wash, and dry to obtain Material Ⅰ;

[0091] S2. Add the Material Ⅰ obtained in step S1 to an aqueous solution containing dodecylmethyldihydroxyethylammonium bromide (4.5 wt%), and then carry out treatment under heating conditions (68 °C, 3.5 h). After the treatment is completed, first carry out centrifugation, washing, and drying, and finally carry out activation (102 °C, 1 h); after the activation is completed, obtain Material Ⅲ; among them, the mass ratio of Material Ⅰ to dodecylmethyldihydroxyethylammonium bromide is 1:0.35;

[0092] S3. Add silicon dioxide to N,N-dimethylformamide (DMF), disperse evenly, then add succinic anhydride and KH550, maintain centrifugal stirring and carry out heating treatment (35 °C, 2 h). After the treatment is completed, carry out centrifugation (100 rpm), washing, and drying to obtain Material Ⅳ; among them, the mass ratio of silicon dioxide, solvent, succinic anhydride, and KH550 is 1:60:2.8:6.5;

[0093] S4. Add titanium dioxide, the Material Ⅲ obtained in step S2, and the Material Ⅳ obtained in step S3 to water according to a mass ratio of 1:0.5:0.65, and carry out stirring treatment under heating conditions (30 °C, 2 h). After the treatment is completed, carry out suction filtration, drying, and grinding to obtain the composite filler.

[0094] In this comparative example, a preparation method of the above high-hardness glaze coating is also provided, including the following steps:

[0095] Mix half of the mass of water, fluorinated silicon propyl emulsion, potassium silicate solution, functional additives (dispersant, defoamer, leveling agent, wetting agent), and film-forming aid, and stir evenly. Then add composite filler and the other half of the mass of water, and stir evenly again to obtain the product.

[0096] Comparative Example 4

[0097] Compared with Example 1, step S4 is omitted in Comparative Example 4, and the rest are the same. Specifically, in this comparative example, a high-hardness glaze coating is provided. Calculated based on 100% by mass percentage, it is prepared from the following raw materials: 22% fluorinated silicon propyl emulsion, 13% potassium silicate solution, 32% composite filler, 0.5% dispersant, 0.4% defoamer, 0.6% leveling agent, 0.6% wetting agent, 3% film-forming aid, and the balance is water.

[0098] Among them, the preparation of the composite filler includes the following steps:

[0099] S1. Mix bentonite and attapulgite in a mass ratio of 1:2, first crush and sieve through 100 meshes, and then treat with 12 wt% hydrochloric acid solution (room temperature, 4 h). After the treatment is completed, filter, wash, and dry to obtain Material I;

[0100] S2. Mix the Material I obtained in step S1 with sodium hydroxide in a mass ratio of 1:0.45, and perform high-temperature treatment (720 °C, 0.5 h). After the treatment is completed, obtain Material II;

[0101] S3. Add the Material II obtained in step S2 to an aqueous solution containing dodecyl methyl dihydroxyethyl ammonium bromide (4.5 wt%), and then perform treatment under heating conditions (68 °C, 3.5 h). After the treatment is completed, first perform centrifugation, washing, and drying, and finally perform activation (102 °C, 1 h); after the activation is completed, obtain Material III; among them, the mass ratio of Material II to dodecyl methyl dihydroxyethyl ammonium bromide is 1:0.35;

[0102] S4. Take silicon dioxide and set it aside;

[0103] S5. Add titanium dioxide, the Material III obtained in step S3, and the silicon dioxide in step S4 to water in a mass ratio of 1:0.5:0.65, and stir under heating conditions (30 °C, 2 h). After the treatment is completed, perform suction filtration, drying, and grinding to obtain the composite filler.

[0104] In this comparative example, a preparation method of the above high-hardness glaze coating is also provided, including the following steps:

[0105] Mix half of the mass of water, fluorosilicone propylene emulsion, potassium silicate solution, functional additives (dispersant, defoamer, leveling agent, wetting agent), and film-forming aid evenly, and then add composite filler and the other half of the mass of water, and stir evenly again.

[0106] Perform performance tests on the glazed coatings prepared in Example 1 and Comparative Examples 1-4 as follows:

[0107] Hardness test: Refer to GB / T 6739-2022.

[0108] Flexibility test: Refer to GB / T1731-2020.

[0109] Weather resistance test: Refer to GB / T 9276-1996.

[0110] Impact resistance test: Refer to GB / T 1732-2020.

[0111] Water resistance test: Refer to GB / T 9755-2014.

[0112] Anti-cracking test: Place the coating at 40°C for 12 h and then at -5°C for 12 h, and observe the surface of the coating.

[0113] The specific test results are shown in Table 1.

[0114] Table 1 Test results of examples and comparative examples

[0115]

[0116]

[0117] As can be seen from Table 1, the glazed coating prepared by the present invention has high hardness, good toughness, good weather resistance and anti-cracking performance, and excellent comprehensive performance.

[0118] It should be particularly emphasized that although only dispersant, defoamer, leveling agent, and wetting agent are used as functional additives in the present invention, other functional additives such as mildew-proof agent and preservative can be flexibly selected and added by those skilled in the art according to actual needs. The description of the above embodiments does not constitute a limitation on the protection scope of the technical solution of the present invention.

[0119] When the glazed coating provided by the present invention is specifically used, the following construction procedures can be adopted:

[0120] (1) Substrate treatment: Remove floating ash and oil stains;

[0121] (2) Wall reinforcement: Apply a coat of odorless, environmentally friendly and water-resistant wall reinforcement agent evenly;

[0122] (3) Joint Sealing: After cleaning the floating dust and debris from the joints between different base materials, the joints of gypsum boards, and the cracks in the walls, use crack-resistant joint king to fill them flat.

[0123] (4) Rough Leveling: For places where the wall surface flatness difference is more than 3 mm, use powdered water-resistant leveling putty for rough leveling.

[0124] (5) Crack-resistant Leveling: Apply two coats of soft porcelain crack-resistant treasure (two-component waterproof flexible crack-resistant smooth putty) all over, controlling the thickness at 1 - 1.5 mm.

[0125] (6) Fine Leveling: Apply wall glaze mud (paste-like water-resistant smooth putty) one or two times and sand it flat.

[0126] (7) Sealing Wall Glaze: Apply one coat of white or transparent penetrating base glaze.

[0127] (8) Apply this product two to three times.

[0128] Although the embodiments of the present invention have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A high-hardness glaze coating, characterized in that: The invention is prepared from the following raw materials by mass percentage: 20-30% fluorinated silicone acrylic emulsion, 5-20% potassium silicate liquid, 8-35% composite filler, 2-8% functional additive, 2-6% film-forming additive, and 20-60% water; The composite filler is prepared from titanium dioxide, silicon dioxide, bentonite and attapulgite as raw materials; The preparation of the composite filler comprises the following steps: S1. Mix bentonite and attapulgite, crush and screen them, and then treat them with hydrochloric acid solution. After the treatment, filter, wash and dry them to obtain material I; S2, mixing the material I obtained in step S1 with sodium hydroxide and then subjecting it to high temperature treatment, after the treatment is completed, obtaining material II; wherein the high temperature treatment temperature is 710-780°C, and the treatment time is 0.5-2h; S3, adding the material II obtained in step S2 to an aqueous solution containing dodecylmethyl dihydroxyethyl ammonium bromide, and then treating it under heating conditions. After the treatment is completed, it is first centrifuged, washed, and dried, and finally activated; after the activation is completed, material III is obtained; S4, adding silicon dioxide to the solvent, and then adding succinic anhydride and KH550 after uniform dispersion, maintaining centrifugal stirring and heating treatment, after the treatment is completed, centrifugation, washing, and drying are performed to obtain material IV; S5, adding titanium dioxide, material III obtained in step S3, and material IV obtained in step S4 into water, stirring under heating conditions, and after the treatment, filtering, drying, and grinding to obtain a composite filler; Wherein, in step S1, the mass ratio of bentonite to attapulgite is 1:1.5-2.5, and the bentonite is sieved through 80-150 mesh; the concentration of the hydrochloric acid solution is 10-15wt%, the temperature of the hydrochloric acid solution treatment is room temperature, and the treatment time is 2-6h; Among them, in step S3, the concentration of dodecylmethyldihydroxyethylammonium bromide is 4-8wt%, and the mass ratio of material II to dodecylmethyldihydroxyethylammonium bromide is 1:0.3-0.6; the heating treatment temperature is 50-70°C, and the treatment time is 1-6h; the activation treatment temperature is 100-110°C, and the activation time is 0.5-4h.

2. A high-hardness glaze coating according to claim 1, characterized in that: In step S2, the mass ratio of material I to sodium hydroxide is 1:0.3-0.

65.

3. A high-hardness glaze coating according to claim 1, characterized in that: In step S4, the solvent is DMF, the mass ratio of silica, solvent, succinic anhydride and KH550 is 1:50-70:2-3.5:5-8; the centrifugal stirring rate is 80-150 rpm; the heating temperature is 30-40° C., and the treatment time is 1-6 h.

4. A high-hardness glaze coating according to claim 1, characterized in that: In step S5, the mass ratio of titanium dioxide, material III, and material IV is 1:0.4-0.7:0.5-0.9; the heating treatment temperature is 25-35°C, and the treatment time is 1-4h.

5. A high-hardness glaze coating according to claim 1, characterized in that: The functional additive is selected from one or more of a dispersant, a defoamer, an antifreeze agent, a wetting agent, a pH regulator, a preservative, a mildew preventer, a leveling agent, and a thickener.

6. A high-hardness glaze coating according to claim 5, characterized in that: The film-forming aid is selected from one or more of propylene glycol, ethylene glycol, and alcohol ester film-forming aids.

7. A method for preparing the high-hardness glaze coating according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: mixing half the mass of water, fluorinated silicone acrylic emulsion, potassium silicate liquid, functional additives and film-forming additives and stirring evenly, then adding composite fillers and the other half the mass of water and stirring evenly again.

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