Mildew-proof and corrosion-resistant waterborne epoxy floor paint and preparation method thereof

Abstract

The invention discloses a mildewproof and anticorrosive waterborne epoxy floor paint and a preparation method thereof, and belongs to the technical field of waterborne paints.The mildewproof and anticorrosive waterborne epoxy floor paint is prepared from, by mass, 45.5%-52.0% of modified waterborne epoxy emulsion, 0.5%-1.5% of a curing agent, 0.5%-1.5% of a curing agent and the balance water. 18.5%-20.0% of a water-based epoxy curing agent; 7.5%-8.5% of a mildew-proof microcapsule; 3.5% to 5.0% of silica powder; 2.5%-3.0% of nano zinc oxide; 0.3%-0.5% of a dispersing agent; 0.1%-0.3% of a defoaming agent; and the balance of deionized water. Aiming at the three technical problems of poor mildew preventive compatibility, insufficient long-term effect and reduced coating mechanical property of the existing water-based epoxy floor paint, the invention provides the water-based epoxy floor paint with long-term mildew and corrosion resistance, high mechanical property and environmental friendliness through material design and process improvement.

Description

Technical Field

[0001] The invention belongs to the technical field of water-based coatings, and particularly relates to a mildew-proof and corrosion-resistant water-based epoxy floor paint and a preparation method thereof. Background Art

[0002] Water-based epoxy floor paints are gradually replacing traditional solvent-based products due to their environmental friendliness and low VOC profile. However, in high-humidity or microbially active environments, existing water-based epoxy floor paints are susceptible to mold and bacteria growth, leading to powdering, discoloration, and even flaking of the coating, seriously affecting its service life and aesthetics.

[0003] The existing technology mainly improves the anti-mildew performance by adding chemical anti-mildew agents (such as isothiazolinones), but there are the following problems:

[0004] 1. Poor compatibility: The mildew inhibitor is unevenly dispersed in the water-based system and easily migrates to the coating surface and becomes ineffective;

[0005] 2. Insufficient long-term effectiveness: A single antifungal agent is easily metabolized and decomposed by microorganisms in a complex environment, and the antifungal period is usually less than 6 months;

[0006] 3. Deterioration of mechanical properties: Excessive addition of antifungal agents will destroy the cross-linking structure of epoxy resin, resulting in reduced adhesion and wear resistance.

[0007] With the surge in demand for clean floors in the medical, food and other industries, it is of great practical significance to develop a water-based epoxy floor paint that has long-lasting mildew and corrosion resistance, high mechanical properties and is environmentally friendly. Summary of the Invention

[0008] The present invention aims to solve the technical problems of poor compatibility, insufficient long-term effectiveness and decreased coating performance of mildew inhibitors in the prior art, and proposes a mildew-proof and anti-corrosion water-based epoxy floor paint and a preparation method thereof.

[0009] The purpose of the present invention can be achieved through the following technical solutions:

[0010] A mildew-proof and anti-corrosion water-based epoxy floor paint, comprising the following raw materials in percentage by weight:

[0011] Modified waterborne epoxy emulsion: 45.5%~52.0%;

[0012] Water-based epoxy curing agent: 18.5% to 20.0%;

[0013] Anti-mildew microcapsules: 7.5% to 8.5%;

[0014] Silica powder: 3.5% to 5.0%;

[0015] Nano zinc oxide: 2.5% to 3.0%;

[0016] Dispersant: 0.3% to 0.5%;

[0017] Defoaming agent: 0.1% to 0.3%;

[0018] The balance was deionized water.

[0019] Furthermore, the anti-mildew microcapsules are prepared by the following steps:

[0020] Weigh gelatin and gum arabic, dissolve them in deionized water respectively, stir in a water bath at 50°C until completely dissolved, to obtain a gelatin solution and a gum arabic solution; then weigh berberine and benzimidazole carbamate, mix them, dissolve them in anhydrous ethanol, and ultrasonically disperse them for 5 minutes to obtain a core material solution; the core material solution is added dropwise to the gelatin solution, high-speed shear emulsification is carried out at 5000r / min for 10 to 20 minutes to form an O / W emulsion, and then the gum arabic solution is added thereto, and stirring is continued for 10 to 20 minutes. After completion, the pH of the system is adjusted to 4.0 to 4.2 with glacial acetic acid. After adjustment, the system is stirred at 40 to 45°C for 1 hour, and then a 10% by mass glutaraldehyde solution is added thereto with stirring, and stirring is continued for 2 hours. After completion, the system is cooled to room temperature, centrifuged to obtain microcapsules, washed three times with deionized water, and then placed at 40°C for vacuum drying for 24 hours to obtain anti-mildew microcapsules.

[0021] Furthermore, the usage ratio of the gelatin, gum arabic, deionized water, berberine, benzimidazole carbamate, anhydrous ethanol, and 10% glutaraldehyde solution is 50g:50g:1L:20g:20g:200mL:40-50mL.

[0022] Furthermore, the modified waterborne epoxy emulsion is prepared by the following steps:

[0023] A hyperbranched epoxy resin and an epoxy emulsifier are added to the epoxy resin. After the addition is completed, the system is heated to 40-50° C. and stirred at a constant temperature for 1-2 hours. After the addition is completed, deionized water is added dropwise to the system, and the system now presents an oil-in-water state. Deionized water is continued to be added dropwise until a phase inversion occurs in the system, that is, the system presents an oil-in-water state. After the addition is completed, the system is cooled to room temperature, stirred at room temperature for 2-4 hours, and then deionized water is added thereto with stirring until the solid content of the system is 55%-60%, and stirred at room temperature for 20-30 minutes to obtain a modified waterborne epoxy emulsion.

[0024] Furthermore, the model of the epoxy resin is E-51; the model of the epoxy emulsifier is WL92.

[0025] Furthermore, the usage ratio of the epoxy resin, the hyperbranched epoxy resin and the epoxy emulsifier is 85-90g:10-15g:10-15g.

[0026] Furthermore, the hyperbranched epoxy resin is prepared by the following steps:

[0027] Ethylene glycol diglycidyl ether and tetrabutylammonium bromide are added to a reactor. After completion, nitrogen is introduced into the reactor. The reactor is heated to 130-135° C. and stirred at a constant temperature for 10-20 minutes. After completion, the reactor is cooled to 100-110° C. and trimethylolpropane is added to the reactor with stirring. The addition rate of the trimethylolpropane is controlled to ensure that the addition is completed within 2 hours. The reactor is heated to 160-170° C. and stirred at a constant temperature until the epoxy value of the system decreases to 0.2 mol / 100 g. After completion, the reactor is cooled to room temperature and the product is collected to obtain a hyperbranched epoxy resin.

[0028] Furthermore, the usage ratio of ethylene glycol diglycidyl ether, tetrabutylammonium bromide and trimethylolpropane is 1 mol:0.05 mol:0.4 mol.

[0029] Furthermore, the preparation method of the mildew-proof and anti-corrosion water-based epoxy floor paint comprises the following steps:

[0030] Weigh the raw materials according to the mass percentage, and use the modified water-based epoxy emulsion as component A; then stir and mix the water-based epoxy curing agent, anti-mildew microcapsules, silicon micropowder, nano zinc oxide, dispersant, defoaming agent and deionized water for 20 to 30 minutes to obtain component B; mix component A and component B, and continue to stir and mix for 20 to 30 minutes to obtain the anti-mildew and anti-corrosion water-based epoxy floor paint.

[0031] Furthermore, the model of the waterborne epoxy curing agent is Anquamine 701; the mesh size of the silicon micropowder is 600 mesh; the particle size of the nano zinc oxide is 50 nm; the model of the dispersant is BYK-190; and the model of the defoaming agent is TEGO Foamex 810.

[0032] Beneficial effects of the present invention:

[0033] This invention addresses the three major technical issues of existing water-based epoxy floor paints: poor compatibility with mildew inhibitors, insufficient long-term effectiveness, and reduced mechanical properties of the coating. Through material design and process improvements, it provides a water-based epoxy floor paint that combines long-term mildew and corrosion resistance with high mechanical properties and is environmentally friendly. Based on test data, the beneficial effects of this invention are specifically reflected in the following aspects:

[0034] 1. Anti-mildew and anti-corrosion performance is significantly improved:

[0035] (1) Synergistic anti-mildew mechanism:

[0036] The present invention prepares mold-resistant microcapsules using a complex coacervation method. The natural mold inhibitor berberine is coated with the chemical mold inhibitor benzimidazole carbamate, resulting in a synergistic broad-spectrum antibacterial effect. As shown in test data, Examples 10-12 all achieved a mold resistance rating of 0 (no mold growth), while Comparative Example 5 (directly adding an uncoated mold inhibitor) achieved a rating of 2 (small colonies), and Comparative Example 7 (using a single mold inhibitor) achieved a rating of 3 (significant colonies). Microencapsulation technology extends the sustained-release period of the mold inhibitor, resolving the issue of the limited long-term effectiveness of traditional mold inhibitors due to rapid migration or degradation.

[0037] (2) Enhanced corrosion resistance:

[0038] The nano-zinc oxide (50 nm) and silicon micropowder (600 mesh) of the present invention synergistically enhance the coating's compactness, resulting in a salt spray corrosion extension width of only 0.1 to 0.5 mm (Examples 10 to 12), significantly superior to Comparative Example 4 (extension width 1.2 to 1.5 mm). The three-dimensional cross-linked network of the hyperbranched epoxy resin (Example 5) effectively isolates moisture from penetrating. Comparative Example 4, which lacks hyperbranching modification, exhibits significantly reduced corrosion resistance.

[0039] 2. Comprehensive optimization of mechanical properties:

[0040] (1) Improved adhesion and wear resistance:

[0041] The introduction of the hyperbranched epoxy resin prepared by the present invention (Examples 1-3) significantly improved the film-forming properties and crosslink density of the emulsion. Example 11 achieved an adhesion of 5B (no shedding), while Comparative Example 4 (unmodified emulsion) only achieved 3B. In the Taber abrasion test, Example 12 exhibited a wear loss of only 12-15 mg, a 65% reduction compared to Comparative Example 4 (35-40 mg). The hyperbranched structure enhances the coating's shear resistance through a mechanical chain effect.

[0042] (2) Breakthrough improvement in water resistance:

[0043] The phase inversion emulsification process of the modified waterborne epoxy emulsion of the present invention (Examples 4-6) stabilizes the solid content at 55%-60%. Combined with the hydrophobic effect of nano-zinc oxide, Examples 10-12 showed no blistering or shedding after 240 hours of immersion in water, while Comparative Example 6 (insufficient cross-linking of microcapsules) exhibited local shedding, and Comparative Example 7 (single antifungal agent) exhibited widespread failure due to poor interfacial compatibility.

[0044] 3. Environmental friendliness:

[0045] The present invention utilizes modified water-based epoxy emulsion to replace the traditional solvent-based system, combines microencapsulation technology to reduce the volatilization of mildew inhibitors, and meets the environmental protection requirements of the medical and food industries for clean floors.

[0046] Conclusion: This invention, through the synergistic combination of hyperbranched epoxy emulsion modification, dual antifungal agent microencapsulation, and nanocomposite reinforcement, comprehensively overcomes the technical bottleneck of existing water-based epoxy floor paints, which struggles to balance antifungal and mechanical properties. Data from the examples confirm that core indicators such as antifungal grade, salt spray corrosion resistance, and adhesion all reach industry-leading levels, while also offering environmental advantages, providing an innovative solution for high-end clean flooring. DETAILED DESCRIPTION

[0047] Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, it is obvious that described embodiment is only a part of embodiment of the present invention, rather than whole embodiment. Based on the embodiment in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work premise all fall within the scope of protection of the present invention. Raw materials, reagents or devices used in the following examples, unless otherwise specified, can be obtained from conventional commercial sources, or can be obtained by existing known methods.

[0048] Example 1

[0049] Preparation of hyperbranched epoxy resin:

[0050] 1 mol of ethylene glycol diglycidyl ether (analytical grade) and 0.05 mol of tetrabutylammonium bromide (analytical grade) were added to the reactor. After completion, nitrogen was introduced thereto. The reactor was then heated to 130° C. and stirred at this constant temperature for 10 min. After completion, the reactor was cooled to 100° C., and 0.4 mol of trimethylolpropane (analytical grade) was added to the reactor with stirring. The addition rate of trimethylolpropane was simultaneously controlled to ensure that the addition was completed within 2 h. The reactor was then heated to 160° C. and stirred at this constant temperature until the epoxide value of the system dropped to 0.2 mol / 100 g. After completion, the reactor was cooled to room temperature, and the product was collected to obtain a hyperbranched epoxy resin.

[0051] Example 2

[0052] Preparation of hyperbranched epoxy resin:

[0053] 1 mol of ethylene glycol diglycidyl ether (analytical grade) and 0.05 mol of tetrabutylammonium bromide (analytical grade) were added to the reactor. After completion, nitrogen was introduced thereto. The reactor was then heated to 130° C. and stirred at this constant temperature for 20 min. After completion, the reactor was cooled to 105° C., and 0.4 mol of trimethylolpropane (analytical grade) was added to the reactor with stirring. The addition rate of trimethylolpropane was simultaneously controlled to ensure that the addition was completed within 2 h. The reactor was then heated to 165° C. and stirred at this constant temperature until the epoxide value of the system dropped to 0.2 mol / 100 g. After completion, the reactor was cooled to room temperature, and the product was collected to obtain a hyperbranched epoxy resin.

[0054] Example 3

[0055] Preparation of hyperbranched epoxy resin:

[0056] 1 mol of ethylene glycol diglycidyl ether (analytical grade) and 0.05 mol of tetrabutylammonium bromide (analytical grade) were added to the reactor. After completion, nitrogen was introduced thereto. The reactor was then heated to 135° C. and stirred at this constant temperature for 20 min. After completion, the reactor was cooled to 110° C., and 0.4 mol of trimethylolpropane (analytical grade) was added to the reactor with stirring. The addition rate of trimethylolpropane was simultaneously controlled to ensure that the addition was completed within 2 h. The reactor was then heated to 170° C. and stirred at this constant temperature until the epoxide value of the system dropped to 0.2 mol / 100 g. After completion, the reactor was cooled to room temperature, and the product was collected to obtain a hyperbranched epoxy resin.

[0057] Example 4

[0058] Preparation of modified waterborne epoxy emulsion:

[0059] To 85 g of epoxy resin (E-51), 10 g of the hyperbranched epoxy resin prepared in Example 1 and 15 g of epoxy emulsifier (WL92) were added. After the addition was completed, the system was heated to 40° C. and stirred at this constant temperature for 1 h. After completion, deionized water was added dropwise to the system. At this time, the system showed an oil-in-water state. Deionized water was continued to be added dropwise until a phase inversion occurred in the system, that is, the system showed an oil-in-water state. After completion, the mixture was cooled to room temperature and stirred at room temperature for 2 h. Deionized water was then added thereto with stirring until the solid content of the system was 55%, and then stirred at room temperature for 20 min to obtain a modified waterborne epoxy emulsion.

[0060] Example 5

[0061] Preparation of modified waterborne epoxy emulsion:

[0062] To 88 g of epoxy resin (E-51), 12 g of the hyperbranched epoxy resin prepared in Example 2 and 20 g of epoxy emulsifier (WL92) were added. After the addition was completed, the system was heated to 45 ° C and stirred at this constant temperature for 2 h. After completion, deionized water was added dropwise to the system. At this time, the system showed an oil-in-water state. Deionized water was continued to be added dropwise until a phase inversion occurred in the system, that is, the system showed an oil-in-water state. After completion, the mixture was cooled to room temperature and stirred at room temperature for 3 h. Deionized water was then added thereto with stirring until the solid content of the system was 58%, and then stirred at room temperature for 30 min to obtain a modified waterborne epoxy emulsion.

[0063] Example 6

[0064] Preparation of modified waterborne epoxy emulsion:

[0065] To 90 g of epoxy resin (E-51), 15 g of the hyperbranched epoxy resin prepared in Example 3 and 20 g of epoxy emulsifier (WL92) were added. After the addition was completed, the system was heated to 50° C. and stirred at this constant temperature for 2 h. After completion, deionized water was added dropwise to the system. At this time, the system showed an oil-in-water state. Deionized water was continued to be added dropwise until a phase inversion occurred in the system, i.e., the system showed an oil-in-water state. After completion, the mixture was cooled to room temperature and stirred at room temperature for 4 h. Deionized water was then added thereto with stirring until the solid content of the system was 60%, and then stirred at room temperature for 30 min to obtain a modified waterborne epoxy emulsion.

[0066] Comparative Example 1

[0067] Comparative Example 1 is the control group of Example 5, except that the raw material "12 g of the hyperbranched epoxy resin prepared in Example 2" in Example 5 is replaced with "12 g of epoxy resin (E-51)", that is, no hyperbranched epoxy resin is added, and the remaining raw materials, raw material amounts and preparation steps are kept consistent with those in Example 5, and a modified water-based epoxy emulsion is finally obtained.

[0068] Example 7

[0069] Preparation of anti-mildew microcapsules:

[0070] A1. Weigh 50 g of gelatin (food grade) and 50 g of gum arabic (food grade), dissolve each in 1 L of deionized water, and stir in a 50°C water bath until completely dissolved to obtain gelatin solution and gum arabic solution.

[0071] A2. Weigh 20 g of berberine (purity ≥ 98%) and 20 g of benzimidazole carbamate (purity ≥ 95%), mix them, dissolve them in 200 mL of anhydrous ethanol, and ultrasonically disperse them for 5 minutes to obtain a core material solution;

[0072] A3. The core material solution was added dropwise to the gelatin solution and emulsified at high shear speed of 5000 r / min for 10 minutes to form an O / W (oil / water) emulsion. The gum arabic solution was then added and stirred for 10 minutes to fully mix the wall materials. After completion, the pH of the system was adjusted to 4.0 with glacial acetic acid. At this time, gelatin and gum arabic underwent complex coagulation due to charge neutralization, wrapping the core material to form a microcapsule prototype. After adjustment, the solution was stirred at 40°C for 1 hour to gradually solidify the capsule wall. 40 mL of a 10% mass fraction glutaraldehyde solution (cross-linking agent) was then added with stirring and stirred for 2 hours to enhance the mechanical strength of the microcapsule wall. After completion, the system was cooled to room temperature and centrifuged (3000 r / min, 10 minutes) to collect the microcapsules. The microcapsules were washed three times with deionized water to remove the uncoated core material and free wall material, and then dried in a vacuum at 40°C for 24 hours to obtain white powdery mildew-proof microcapsules.

[0073] Example 8

[0074] Preparation of anti-mildew microcapsules:

[0075] A1. Weigh 50 g of gelatin (food grade) and 50 g of gum arabic (food grade), dissolve each in 1 L of deionized water, and stir in a 50°C water bath until completely dissolved to obtain gelatin solution and gum arabic solution.

[0076] A2. Weigh 20 g of berberine (purity ≥ 98%) and 20 g of benzimidazole carbamate (purity ≥ 95%), mix them, dissolve them in 200 mL of anhydrous ethanol, and ultrasonically disperse them for 5 minutes to obtain a core material solution;

[0077] A3. The core material solution was added dropwise to the gelatin solution and emulsified at high shear speed of 5000 r / min for 20 min to form an O / W (oil / water) emulsion. The gum arabic solution was then added and stirred for 20 min to fully mix the wall materials. After completion, the pH of the system was adjusted to 4.0 with glacial acetic acid. At this time, gelatin and gum arabic underwent complex coagulation due to charge neutralization, wrapping the core material to form a microcapsule prototype. After adjustment, the solution was stirred at 45°C for 1 h to gradually solidify the capsule wall. 45 mL of a 10% mass fraction glutaraldehyde solution (cross-linking agent) was then added with stirring and stirred for 2 h to enhance the mechanical strength of the microcapsule wall. After completion, the system was cooled to room temperature and centrifuged (3000 r / min, 10 min) to collect the microcapsules. The microcapsules were washed three times with deionized water to remove the uncoated core material and free wall material, and then vacuum dried at 40°C for 24 h to obtain white powdery mildew-proof microcapsules.

[0078] Example 9

[0079] Preparation of anti-mildew microcapsules:

[0080] A1. Weigh 50 g of gelatin (food grade) and 50 g of gum arabic (food grade), dissolve each in 1 L of deionized water, and stir in a 50°C water bath until completely dissolved to obtain gelatin solution and gum arabic solution.

[0081] A2. Weigh 20 g of berberine (purity ≥ 98%) and 20 g of benzimidazole carbamate (purity ≥ 95%), mix them, dissolve them in 200 mL of anhydrous ethanol, and ultrasonically disperse them for 5 minutes to obtain a core material solution;

[0082] A3. The core material solution was added dropwise to the gelatin solution and emulsified at high shear speed of 5000 r / min for 20 minutes to form an O / W (oil / water) emulsion. The gum arabic solution was then added and stirred for 20 minutes to fully mix the wall materials. After completion, the pH of the system was adjusted to 4.2 with glacial acetic acid. At this time, gelatin and gum arabic underwent complex coagulation due to charge neutralization, wrapping the core material to form a microcapsule prototype. After adjustment, the solution was stirred at 45°C for 1 hour to gradually solidify the capsule wall. 50 mL of a 10% mass fraction glutaraldehyde solution (cross-linking agent) was then added with stirring and stirred for 2 hours to enhance the mechanical strength of the microcapsule wall. After completion, the system was cooled to room temperature and centrifuged (3000 r / min, 10 minutes) to collect the microcapsules. The microcapsules were washed three times with deionized water to remove the uncoated core material and free wall material, and then vacuum dried at 40°C for 24 hours to obtain white powdery mildew-proof microcapsules.

[0083] Comparative Example 2

[0084] Comparative Example 2 is the control group of Example 8. The amount of the raw material "45 mL of 10% mass fraction glutaraldehyde solution (cross-linking agent)" in Example 8 was changed to "25 mL". The remaining raw materials, raw material amounts and preparation steps remained the same as in Example 8, and finally anti-mildew microcapsules were obtained.

[0085] Comparative Example 3

[0086] Comparative Example 3 is the control group of Example 8, except that the raw material "20 g of berberine (purity ≥98%)" in Example 8 is replaced with "20 g of benzimidazole carbamate (purity ≥95%)", that is, a single mildew inhibitor is used, and the remaining raw materials, raw material amounts and preparation steps remain the same as in Example 8, and mildew-proof microcapsules are finally obtained.

[0087] Example 10

[0088] Preparation of mildew-proof and anti-corrosion water-based epoxy floor paint:

[0089] First, the above-mentioned floor paint includes the following raw materials in percentage by mass:

[0090] Modified waterborne epoxy emulsion prepared in Example 4: 45.5%;

[0091] Water-based epoxy curing agent (Anquamine 701): 18.5%;

[0092] Anti-mildew microcapsules prepared in Example 7: 7.5%;

[0093] Silica powder (600 mesh): 3.5%;

[0094] Nano zinc oxide (50nm): 2.5%;

[0095] Dispersant (BYK-190): 0.3%;

[0096] Defoamer (TEGO Foamex 810): 0.1%;

[0097] The balance was deionized water.

[0098] Then, the preparation method of the above-mentioned floor paint comprises the following steps:

[0099] Weigh the raw materials according to the mass percentage, and use the modified water-based epoxy emulsion prepared in Example 4 as component A; then stir and mix the water-based epoxy curing agent, the mildew-proof microcapsules prepared in Example 7, silica powder, nano zinc oxide, dispersant, defoaming agent and deionized water for 20 minutes to obtain component B; mix component A and component B, and continue stirring and mixing for 20 minutes to obtain a mildew-proof and anti-corrosion water-based epoxy floor paint.

[0100] Example 11

[0101] Preparation of mildew-proof and anti-corrosion water-based epoxy floor paint:

[0102] First, the above-mentioned floor paint includes the following raw materials in percentage by mass:

[0103] Modified waterborne epoxy emulsion prepared in Example 5: 50%;

[0104] Water-based epoxy curing agent (Anquamine701): 20%;

[0105] Anti-mildew microcapsules prepared in Example 8: 8%;

[0106] Silica powder (600 mesh): 4%;

[0107] Nano zinc oxide (50nm): 3.0%;

[0108] Dispersant (BYK-190): 0.5%;

[0109] Defoamer (TEGO Foamex 810): 0.2%;

[0110] The balance was deionized water.

[0111] Then, the preparation method of the above-mentioned floor paint comprises the following steps:

[0112] Weigh the raw materials according to the mass percentage, and use the modified water-based epoxy emulsion prepared in Example 5 as component A; then stir and mix the water-based epoxy curing agent, the mildew-proof microcapsules prepared in Example 8, silica powder, nano zinc oxide, dispersant, defoaming agent and deionized water for 30 minutes to obtain component B; mix component A and component B, and continue stirring and mixing for 30 minutes to obtain a mildew-proof and anti-corrosion water-based epoxy floor paint.

[0113] Example 12

[0114] Preparation of mildew-proof and anti-corrosion water-based epoxy floor paint:

[0115] First, the above-mentioned floor paint includes the following raw materials in percentage by mass:

[0116] Modified waterborne epoxy emulsion prepared in Example 6: 52.0%;

[0117] Water-based epoxy curing agent (Anquamine 701): 20.0%;

[0118] Anti-mildew microcapsules prepared in Example 9: 8.5%;

[0119] Silica powder (600 mesh): 5.0%;

[0120] Nano zinc oxide (50nm): 3.0%;

[0121] Dispersant (BYK-190): 0.5%;

[0122] Defoamer (TEGO Foamex 810): 0.3%;

[0123] The balance was deionized water.

[0124] Then, the preparation method of the above-mentioned floor paint comprises the following steps:

[0125] Weigh the raw materials according to the mass percentage, and use the modified water-based epoxy emulsion prepared in Example 6 as component A; then stir and mix the water-based epoxy curing agent, the mildew-proof microcapsules prepared in Example 9, silica powder, nano zinc oxide, dispersant, defoaming agent and deionized water for 30 minutes to obtain component B; mix component A and component B, and continue stirring and mixing for 30 minutes to obtain a mildew-proof and anti-corrosion water-based epoxy floor paint.

[0126] Comparative Example 4

[0127] Comparative Example 4 is the control group of Example 11. The raw material "modified water-based epoxy emulsion prepared in Example 5" in Example 11 is replaced by "modified water-based epoxy emulsion prepared in Comparative Example 1", and the remaining raw materials, raw material amounts and preparation steps remain the same as in Example 11, and finally an anti-mildew and anti-corrosion water-based epoxy floor paint is obtained.

[0128] Comparative Example 5

[0129] Comparative Example 5 is the control group of Example 11, except that the raw material "the anti-mildew microcapsules prepared in Example 8" in Example 11 is replaced by "berberine and benzimidazole carbamate in equal mass ratio", that is, the microcapsule structure is removed, and the remaining raw materials, raw material amounts and preparation steps remain the same as in Example 11, and finally an anti-mildew and anti-corrosion water-based epoxy floor paint is obtained.

[0130] Comparative Example 6

[0131] Comparative Example 6 is the control group of Example 11. The raw material "anti-mildew microcapsules prepared in Example 8" in Example 11 is replaced by "anti-mildew microcapsules prepared in Comparative Example 2", that is, the microcapsule structure is removed, and the remaining raw materials, raw material amounts and preparation steps remain the same as in Example 11, and finally an anti-mildew and anti-corrosion water-based epoxy floor paint is obtained.

[0132] Comparative Example 7

[0133] Comparative Example 7 is the control group of Example 11. The raw material "anti-mildew microcapsules prepared in Example 8" in Example 11 is replaced by "anti-mildew microcapsules prepared in Comparative Example 3", that is, the microcapsule structure is removed, and the remaining raw materials, raw material amounts and preparation steps remain the same as in Example 11, and finally an anti-mildew and anti-corrosion water-based epoxy floor paint is obtained.

[0134] Test Example 1

[0135] The mildew-proof and anti-corrosion water-based epoxy floor paints prepared in Examples 10 to 12 and Comparative Examples 4 to 7 were respectively applied to the surface of a 50 cm × 50 cm flat plate and dried at room temperature for 24 hours to form a 2 mm paint sample. The paint sample was then subjected to a performance test. The performance test process is as follows, and the test results are shown in Table 1:

[0136] (1) Mildew resistance grade (GB / T 1741-2020): Paint samples were inoculated with five types of molds, including Aspergillus niger, and cultured at 28°C / 95% RH for 28 days. The samples were evaluated on a scale of 0 to 4 (0: no growth; 4: full coverage).

[0137] (2) Salt spray corrosion resistance (ASTM B117): The scratched paint sample was exposed to a 5% NaCl fog box, and the rust extension width (mm) was recorded after 720 h.

[0138] (3) Adhesion (GB / T 9286-2021): Cross-hatch method (1 mm spacing), after the tape is peeled off, observe the peeling area on the paint sample (0 to 5B, 5B is the best).

[0139] (4) Abrasion resistance (GB / T 1768-2006): Taber abrader (500 g / wheel, 1000 revolutions), mass loss (mg).

[0140] (5) Water resistance (GB / T 1733-1993): After immersion in water for 240 hours, observe the paint sample for blistering and peeling.

[0141] Table 1 Test results

[0142]

[0143] It should be noted that, in this document, terms such as "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements that are inherent to such process, method, article or apparatus.

[0144] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A mildew-proof and anti-corrosion water-based epoxy floor paint, characterized in that: Including the following raw materials by mass percentage: Modified waterborne epoxy emulsion: 45.5%~52.0%; Water-based epoxy curing agent: 18.5% to 20.0%; Anti-mildew microcapsules: 7.5% to 8.5%; Silica powder: 3.5% to 5.0%; Nano zinc oxide: 2.5% to 3.0%; Dispersant: 0.3% to 0.5%; Defoaming agent: 0.1% to 0.3%; The balance was deionized water.

2. The mildew-proof and corrosion-resistant water-based epoxy floor paint according to claim 1, characterized in that: The anti-mildew microcapsules are prepared by the following steps: Weigh gelatin and gum arabic, dissolve them in deionized water respectively, stir in a water bath at 50°C until completely dissolved, to obtain a gelatin solution and a gum arabic solution; then weigh berberine and benzimidazole carbamate, mix them, dissolve them in anhydrous ethanol, and ultrasonically disperse them for 5 minutes to obtain a core material solution; the core material solution is added dropwise to the gelatin solution, high-speed shear emulsification is carried out at 5000r / min for 10 to 20 minutes to form an O / W emulsion, and then the gum arabic solution is added thereto, and stirring is continued for 10 to 20 minutes. After completion, the pH of the system is adjusted to 4.0 to 4.2 with glacial acetic acid. After adjustment, the system is stirred at 40 to 45°C for 1 hour, and then a 10% by mass glutaraldehyde solution is added thereto with stirring, and stirring is continued for 2 hours. After completion, the system is cooled to room temperature, centrifuged to obtain microcapsules, washed three times with deionized water, and then placed at 40°C for vacuum drying for 24 hours to obtain anti-mildew microcapsules.

3. The mildew-proof and corrosion-resistant water-based epoxy floor paint according to claim 2, characterized in that: The usage ratio of the gelatin, gum arabic, deionized water, berberine, benzimidazole carbamate, anhydrous ethanol, and 10% glutaraldehyde solution is 50g:50g:1L:20g:20g:200mL:40-50mL.

4. The mildew-proof and corrosion-resistant water-based epoxy floor paint according to claim 1, characterized in that: The modified waterborne epoxy emulsion is prepared by the following steps: A hyperbranched epoxy resin and an epoxy emulsifier are added to the epoxy resin. After the addition is completed, the system is heated to 40-50° C. and stirred at a constant temperature for 1-2 hours. After the addition is completed, deionized water is added dropwise to the system, and the system now presents an oil-in-water state. Deionized water is continued to be added dropwise until a phase inversion occurs in the system, that is, the system presents an oil-in-water state. After the addition is completed, the system is cooled to room temperature, stirred at room temperature for 2-4 hours, and then deionized water is added thereto with stirring until the solid content of the system is 55%-60%, and stirred at room temperature for 20-30 minutes to obtain a modified waterborne epoxy emulsion.

5. The mildew-proof and corrosion-resistant water-based epoxy floor paint according to claim 4, characterized in that: The model of the epoxy resin is E-51; the model of the epoxy emulsifier is WL92.

6. The mildew-proof and corrosion-resistant water-based epoxy floor paint according to claim 4, characterized in that: The usage ratio of the epoxy resin, the hyperbranched epoxy resin and the epoxy emulsifier is 85-90g:10-15g:10-15g.

7. The mildew-proof and corrosion-resistant water-based epoxy floor paint according to claim 4, characterized in that: The hyperbranched epoxy resin is prepared by the following steps: Ethylene glycol diglycidyl ether and tetrabutylammonium bromide are added to a reactor. After completion, nitrogen is introduced into the reactor. The reactor is heated to 130-135° C. and stirred at a constant temperature for 10-20 minutes. After completion, the reactor is cooled to 100-110° C. and trimethylolpropane is added to the reactor with stirring. The addition rate of the trimethylolpropane is controlled to ensure that the addition is completed within 2 hours. The reactor is heated to 160-170° C. and stirred at a constant temperature until the epoxy value of the system decreases to 0.2 mol / 100 g. After completion, the reactor is cooled to room temperature and the product is collected to obtain a hyperbranched epoxy resin.

8. The mildew-proof and corrosion-resistant water-based epoxy floor paint according to claim 7, characterized in that: The usage ratio of ethylene glycol diglycidyl ether, tetrabutylammonium bromide and trimethylolpropane is 1 mol:0.05 mol:0.4 mol.

9. The method for preparing a mildew-proof and anti-corrosion waterborne epoxy floor paint according to any one of claims 1 to 8, characterized in that: The following steps are involved: Weigh the raw materials according to the mass percentage, and use the modified water-based epoxy emulsion as component A; then stir and mix the water-based epoxy curing agent, anti-mildew microcapsules, silicon micropowder, nano zinc oxide, dispersant, defoaming agent and deionized water for 20 to 30 minutes to obtain component B; mix component A and component B, and continue to stir and mix for 20 to 30 minutes to obtain the anti-mildew and anti-corrosion water-based epoxy floor paint.

10. The method for preparing a mildew-proof and anti-corrosion waterborne epoxy floor paint according to claim 9, wherein: The model of the waterborne epoxy curing agent is Anquamine 701; the mesh size of the silicon micropowder is 600 mesh; the particle size of the nano zinc oxide is 50 nm; the model of the dispersant is BYK-190; and the model of the defoaming agent is TEGO Foamex 810.

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