Moisture-resistant mildew-proof wall cloth coating and preparation method thereof

Abstract

The invention relates to a moisture-resistant mildew-proof wall cloth coating and a preparation method thereof, and belongs to the technical field of coatings. The invention relates to a preparation method of a moisture-resistant and mildew-proof wall cloth coating, the moisture-resistant and mildew-proof wall cloth coating is obtained by curing a moisture-resistant and mildew-proof wall cloth coating, and the moisture-resistant and mildew-proof wall cloth coating is prepared by the following steps: in an inert gas environment, stirring and mixing isocyanate, an organic tin catalyst, hydroquinone and ethyl acetate, adding polyether glycol, heating, stirring and carrying out rotary evaporation to obtain a prepolymer; and stirring and mixing the antibacterial agent, the prepolymer, the reaction monomer, the photoinitiator and the auxiliary agent, grinding and filtering to obtain the antibacterial coating. Through the synergistic effect mechanism of the nano-silver, zinc oxide, methacrylic acid, cinnamic acid and hydroxyethyl methacrylic acid phosphate in the moisture-resistant and mildew-proof wall cloth coating, the moisture resistance and mildew-proof performance of the coating are jointly improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of coating, and relates to a moisture-resistant and mildew-resistant wall cloth coating and a preparation method thereof. BACKGROUND

[0002] With the continuous growth of the demand for green and functional indoor decoration materials, wall cloth is widely used in residential, commercial space and public building fields due to its aesthetics and practicality. However, in the humid environment such as the plum rain season in the south and the surrounding of the bathroom, the traditional wall cloth coating is prone to water penetration, which leads to the problem of mold breeding. The organic acid produced by the metabolism of mold will erode the coating matrix, causing the coating to appear conditions such as blistering, peeling and discoloration. In addition, the spread of mold spores will also harm human health.

[0003] Nano-silver is a metal silver nano material with a particle size of 1-100 nanometers. Due to its high specific surface area, excellent chemical activity and unique quantum size effect, it has become a widely used high-efficiency antibacterial agent in the field of high polymer coating. However, the traditional coating which simply relies on inorganic antibacterial agents (such as metal antibacterial agents) has problems such as easy aggregation of antibacterial components, poor compatibility with organic matrix, and insufficient long-acting due to too fast release of metal ions. SUMMARY

[0004] The purpose of the present application is to provide a moisture-resistant and mildew-resistant wall cloth coating and a preparation method thereof. The present application improves the moisture resistance and mildew resistance of the coating through the synergistic mechanism of nano-silver, zinc oxide, methacrylic acid, cinnamic acid and hydroxyethyl methacrylic acid phosphate in the moisture-resistant and mildew-resistant wall cloth coating.

[0005] The purpose of the present application can be achieved by the following technical solutions: A preparation method of a moisture-resistant and mildew-resistant wall cloth coating, the moisture-resistant and mildew-resistant wall cloth coating is obtained after curing of a moisture-resistant and mildew-resistant wall cloth coating, and the moisture-resistant and mildew-resistant wall cloth coating comprises the following steps: Step one, in an inert gas environment, isocyanate, organic tin catalyst, hydroquinone and ethyl acetate are stirred and mixed, polyether glycol is added and heated and stirred, rotary evaporation is performed, and a prepolymer is obtained; Step two, the antibacterial agent, the prepolymer, the reaction monomer, the photoinitiator and the additive are stirred and mixed, ground, filtered, and obtained.

[0006] As a preferred technical solution of the present application, the inert gas environment in step one is a nitrogen environment, the stirring and mixing is stirring at a speed of 500-600 rpm for 20-30 min, and the heating and stirring is stirring at a temperature of 62-70℃ for 4-5h.

[0007] As a preferred technical scheme of the present application, the mass ratio of the isocyanate, ethyl acetate, organic tin catalyst, hydroquinone and polyether polyol in step one is 72-85: 50-60: 0.05-0.07: 0.02-0.03: 30-36, the isocyanate is isophorone diisocyanate, the organic tin catalyst is dibutyl tin diacetate, and the polyether diol is polyether polyol DL-3000D (Lansing East) with a functionality of 2 and a molecular weight of 3000.

[0008] As a preferred technical scheme of the present application, the reaction monomer in step two is mixed by ethyl methacrylate, methacrylic acid and isobornyl acrylate in a mass ratio of 10-12: 3.0-4.2: 1.0-1.3; the mass ratio of the antibacterial agent, prepolymer, reaction monomer, photoinitiator and auxiliary agent is 8-10: 45-55: 100-110: 2.5-3.0: 2-3.

[0009] As a preferred technical scheme of the present application, the photoinitiator in step two is photoinitiator 1173, the auxiliary agent is mixed by defoaming agent and leveling agent in a mass ratio of 1:5, the defoaming agent is BYK-020, and the leveling agent is BYK-3455.

[0010] As a preferred technical scheme of the present application, the stirring mixing in step two is stirring for 30-40 min at 30-40℃; the grinding time is 1.5-2.0 h.

[0011] As a preferred technical scheme of the present application, the preparation method of the antibacterial agent comprises the following steps: A1, uniformly mixing the antibacterial filler and anhydrous ethanol, adding a silane coupling agent and heating to react, filtering the solid material, washing, vacuum drying to obtain an intermediate material; A2, mixing the intermediate material and anhydrous ethanol under an inert gas environment, ultrasonic treatment, adding a composite monomer and an initiator and heating and stirring, centrifuging, washing, vacuum drying to obtain the antibacterial agent.

[0012] As a preferred technical scheme of the present application, the mass ratio of the antibacterial filler, anhydrous ethanol and silane coupling agent in step A1 is 11-13: 40-50: 4.0-5.2, the antibacterial filler is mixed by nano-silver and zinc oxide in a mass ratio of 5:1, the silane coupling agent is vinyl triethoxysilane, the heating reaction is at 50-60℃ for 5-6 h, the washing is with anhydrous ethanol for 3 times, and the vacuum drying is at 80℃ until the weight is constant.

[0013] As a preferred technical scheme of the present application, the composite monomer in step A2 is mixed by mass ratio of 6-8:2-3:1.0-1.4 of methacrylic acid, cinnamic acid and hydroxyethyl methacrylate phosphate, the initiator is initiator AIBN, and the mass ratio of the intermediate material, anhydrous ethanol, composite monomer and initiator is 8-10:20-30:2.0-2.4:0.06-0.08, and the CAS number of the hydroxyethyl methacrylate phosphate is 52628-03-2.

[0014] As a preferred technical scheme of the present application, the ultrasonic treatment in step A2 is 10-15 min of ultrasonic treatment at 300-400 W; and the heating and stirring is 6-8 h of heating and stirring at 60-65 DEG C.

[0015] The present application has the following beneficial effects: 1. The present application destroys the cell membrane structure and metabolic function of microorganisms by releasing silver ions and zinc ions through the antibacterial filler nano-silver and zinc oxide, and the active free radicals generated by the photocatalysis of ZnO oxidize and decompose the microbial components, and the cinnamic acid, which is a natural antibacterial component, enhances the antibacterial effect of nano-silver and zinc oxide, and the graft modification of methacrylic acid and hydroxyethyl methacrylate phosphate improves the dispersibility and long-term effect of inorganic antibacterial components, significantly improving the antibacterial and mildew-proof effect of the coating.

[0016] 2. The present application reduces the internal humid microenvironment of the coating by improving the moisture resistance, and inhibits the breeding of mold from the source, and the long-term effect of the mildew-proof component avoids the erosion of the coating by the metabolic products of mold, further protecting the integrity of the moisture-resistant structure. DETAILED DESCRIPTION

[0017] In order to further illustrate the technical means and effects adopted by the present application to achieve the predetermined application purpose, the specific embodiments, structures, features and effects according to the present application are described in detail as follows in combination with examples.

[0018] Example 1 A preparation method of a moisture-resistant and mildew-proof wall cloth coating comprises the following steps: Step one, under a nitrogen environment, isophorone diisocyanate, dibutyl tin diacetate, hydroquinone and ethyl acetate are stirred at a speed of 500 rpm for 20 min, polyether glycol is stirred at a temperature of 62 DEG C for 4 h, and a prepolymer is obtained by rotary evaporation; the mass ratio of the isophorone diisocyanate, ethyl acetate, dibutyl tin diacetate, hydroquinone and polyether polyol is 72:50:0.05:0.02:30; Step two, the antibacterial agent, prepolymer, reaction monomer, photoinitiator 1173 and auxiliary stirring 30 min at 30 DEG C, grinding 1.5 h, filtration, obtained;The reaction monomer is by ethyl methacrylate, methacrylic acid and isobornyl acrylate mixed in a mass ratio of 10:3.0:1.0;The mass ratio of the antibacterial agent, prepolymer, reaction monomer, photoinitiator 1173 and auxiliary agent is 8:45:100:2.5:2, the auxiliary agent is by defoaming agent and leveling agent mixed in a mass ratio of 1:5; The preparation method of the antibacterial agent comprises the following steps: A1, the antibacterial filler and anhydrous ethanol are uniformly mixed, vinyl triethoxysilane is added and reacted at 50 DEG C for 5 h, the solid material is taken out after filtration, washed with anhydrous ethanol for 3 times, and dried at 80 DEG C under vacuum until constant weight to obtain an intermediate material;The mass ratio of the antibacterial filler, anhydrous ethanol and vinyl triethoxysilane is 11:40:4.0, and the antibacterial filler is a mixture of nano-silver and zinc oxide in a mass ratio of 5:1; A2, under the nitrogen environment, the intermediate material and anhydrous ethanol are mixed, ultrasonic is performed at 300 W for 10 min, the composite monomer and initiator AIBN are added, and stirring is performed at 60 DEG C for 6 h, centrifugation is performed, washed with anhydrous ethanol for 3 times, and dried at 80 DEG C under vacuum until constant weight to obtain the antibacterial agent;The composite monomer is a mixture of methacrylic acid, cinnamic acid and hydroxyethyl methacrylic acid phosphate in a mass ratio of 6:2:1.0, and the mass ratio of the intermediate material, anhydrous ethanol, composite monomer and initiator is 8:20:2.0:0.06.

[0019] Example 2 A preparation method of a moisture-resistant mildew-resistant wall cloth coating comprises the following steps: Step one, under the nitrogen environment, isophorone diisocyanate, dibutyl tin diacetate, hydroquinone and ethyl acetate are stirred at a speed of 550 rpm for 25 min, polyether glycol is added and stirred at a temperature of 66 DEG C for 4.5 h, and rotary evaporation is performed to obtain a prepolymer;The mass ratio of isophorone diisocyanate, ethyl acetate, dibutyl tin diacetate, hydroquinone and polyether polyol is 78:55:0.06:0.025:33; Step two, the antibacterial agent, prepolymer, reaction monomer, photoinitiator 1173 and auxiliary stirring 30 min at 30 DEG C, grinding 1.5 h, filtration, obtained;The reaction monomer is by ethyl methacrylate, methacrylic acid and isobornyl acrylate mixed in a mass ratio of 10:3.0:1.0;The mass ratio of the antibacterial agent, prepolymer, reaction monomer, photoinitiator 1173 and auxiliary agent is 8:45:100:2.5:2, the auxiliary agent is by defoaming agent and leveling agent mixed in a mass ratio of 1:5; The preparation method of the antibacterial agent comprises the following steps: A1, the antibacterial filler and anhydrous ethanol were mixed, vinyl triethoxysilane was added and reacted at 55℃ for 5.5h, the solid material was filtered, washed with anhydrous ethanol for 3 times, and dried at 80℃ under vacuum to constant weight to obtain an intermediate material; the mass ratio of the antibacterial filler, anhydrous ethanol and vinyl triethoxysilane was 12:45:4.6, and the antibacterial filler was a mixture of nano-silver and zinc oxide in a mass ratio of 5:1; A2, the intermediate material and anhydrous ethanol were mixed under a nitrogen environment, ultrasonic treatment was carried out at 350W for 12min, the composite monomer and initiator AIBN were added, and heating and stirring were carried out at 62℃ for 7h, centrifugation was carried out, washing with anhydrous ethanol was carried out for 3 times, and drying was carried out at 80℃ under vacuum to constant weight to obtain the product; the composite monomer was a mixture of methyl methacrylate, cinnamic acid and hydroxyethyl methacrylate phosphate in a mass ratio of 7:2.5:1.2, and the mass ratio of the intermediate material, anhydrous ethanol, composite monomer and initiator was 9:25:2.2:0.07.

[0020] Example 3 A preparation method of a moisture-resistant and mildew-resistant wall cloth coating includes the following steps: Step one, under a nitrogen environment, isophorone diisocyanate, dibutyl tin diacetate, hydroquinone and ethyl acetate were stirred at a speed of 600rpm for 30min, polyether glycol was added and stirred at a temperature of 70℃ for 5h, and rotary evaporation was carried out to obtain a prepolymer; the mass ratio of isophorone diisocyanate, ethyl acetate, dibutyl tin diacetate, hydroquinone and polyether polyol was 85:60:0.07:0.03:36; Step two, the antibacterial agent, the prepolymer, the reaction monomer, the photoinitiator 1173 and the auxiliary agent were stirred at 40℃ for 40min, and grinding was carried out for 2.0h, and then filtration was carried out to obtain the product; the reaction monomer was a mixture of ethyl methacrylate, methacrylic acid and isobornyl acrylate in a mass ratio of 12:4.2:1.3; the mass ratio of the antibacterial agent, the prepolymer, the reaction monomer, the photoinitiator 1173 and the auxiliary agent was 10:55:110:3.0:3, and the auxiliary agent was a mixture of defoaming agent and leveling agent in a mass ratio of 1:5; The preparation method of the antibacterial agent includes the following steps: A1, the antibacterial filler and anhydrous ethanol were mixed, vinyl triethoxysilane was added and reacted at 60℃ for 6h, the solid material was filtered, washed with anhydrous ethanol for 3 times, and dried at 80℃ under vacuum to constant weight to obtain an intermediate material; the mass ratio of the antibacterial filler, anhydrous ethanol and vinyl triethoxysilane was 13:50:5.2, and the antibacterial filler was a mixture of nano-silver and zinc oxide in a mass ratio of 5:1; A2, under nitrogen environment, the intermediate material and anhydrous ethanol were mixed, and ultrasonic was conducted for 15 min at 400 W, and then the composite monomer and initiator AIBN were added, and stirring was conducted at 65℃ for 8 h, centrifugation was conducted, and washing was conducted with anhydrous ethanol for 3 times, and drying was conducted at 80℃ under vacuum until the constant weight was obtained, and the coating material was obtained; the composite monomer was obtained by mixing methyl methacrylate, cinnamic acid and hydroxyethyl methacrylate phosphate according to a mass ratio of 8:3:1.4, and the mass ratio of the intermediate material, anhydrous ethanol, composite monomer and initiator was 10:30:2.4:0.08.

[0021] Comparative Example 1 Comparative Example 1 is different from Example 3 in that cinnamic acid is not used in Comparative Example 1, and the rest is the same.

[0022] Comparative Example 2 Comparative Example 2 is different from Example 3 in that hydroxyethyl methacrylate phosphate is not used in Comparative Example 2, and the rest is the same.

[0023] The coating materials prepared in Examples 1-3 and Comparative Examples 1-2 were respectively subjected to the following performance tests.

[0024] Mold resistance test: according to GB / T1741-2007, the sample was placed in an environment with a temperature of 28℃ and a relative humidity of 95% for 28 days, and the mold growth was observed and rated.

[0025] Antibacterial performance test: according to GB / T21866-2008 (the strain is Staphylococcus aureus).

[0026] Table 1: Performance test results of samples From the test results in Table 1, compared with Comparative Examples 1-2, Examples 1-3 have the synergistic mechanism of nano-silver, zinc oxide, methyl methacrylate, cinnamic acid and hydroxyethyl methacrylate phosphate in the moisture-resistant and mold-resistant wall cloth coating, and each substance improves the moisture resistance and mold resistance of the coating through different chemical action paths.

[0027] The application uses nano-silver and zinc oxide as inorganic antibacterial and mildew-proof fillers, and then uses the composite monomers of methacrylic acid, cinnamic acid and hydroxyethyl methacrylic acid phosphate to chemically bond the inorganic antibacterial and mildew-proof fillers, wherein the cinnamic acid is a natural organic antibacterial component, the composite inorganic antibacterial and mildew-proof fillers can effectively inhibit bacterial reproduction, the hydrophobic property of the benzene ring reduces the water adsorption on the surface of the coating, the double bond participates in free radical polymerization to improve the crosslinking density of the coating, reduces the water penetration channel, the active hydroxyl contained in the hydroxyethyl methacrylic acid phosphate can chemically react with isocyanate, enhances the interfacial bonding force between the antibacterial filler and the coating matrix to avoid the antibacterial component from falling off, the antibacterial and mildew-proof fillers are fixed in the coating network through the participation of the double bond in polymerization, the phosphoric acid ester group and the hydroxyl form hydrogen bonds or coordination bonds, the similarity of the structure of the methacrylic acid phase and the reaction monomer of the system, the coating density and the interfacial bonding strength can be significantly improved, the water penetration path is prolonged, the P-O bond with high bond energy of the phosphoric acid ester group endows the coating with excellent hydrolysis resistance, and the dense network formed by the crosslinking of the double bond further blocks the water penetration.

[0028] The above is only the preferred embodiment of the present application, and does not limit the present application in any form. Although the present application has been disclosed as above, it is not intended to limit the present application. Any person skilled in the art can make some changes or modifications to the above disclosed technical content without departing from the scope of the technical solution of the present application, and any indirect modification, equivalent change and modification of the above embodiment according to the technical essence of the present application still belong to the scope of the technical solution of the present application.

Claims

1. A method for preparing a moisture-resistant mold-resistant wall cloth coating, characterized by, The moisture-resistant and mildew-proof wall cloth coating is obtained after curing of the moisture-resistant and mildew-proof wall cloth coating, which comprises the following steps: Step one, under inert gas environment, isocyanate, organic tin catalyst, hydroquinone and ethyl acetate are stirred and mixed, polyether glycol is added and heated and stirred, rotary evaporation is performed to obtain a prepolymer; Step two, the antibacterial agent, the prepolymer, the reaction monomer, the photoinitiator and the auxiliary agent are stirred and mixed, ground, filtered, and obtained; The preparation method of the antibacterial agent comprises the following steps: A1, the antibacterial filler and anhydrous ethanol are mixed, a silane coupling agent is added and heated to react, the solid material is filtered, washed, and vacuum dried to obtain an intermediate material; A2, under inert gas environment, the intermediate material and anhydrous ethanol are mixed, ultrasonic treatment is performed, a composite monomer and an initiator are added and heated and stirred, centrifuged, washed, and vacuum dried to obtain.

2. The method for preparing a moisture-resistant and mildew-resistant wall cloth coating according to claim 1, characterized in that: The mass ratio of the isocyanate, ethyl acetate, organic tin catalyst, hydroquinone and polyether polyol in step one is 72-85:50-60:0.05-0.07:0.02-0.03:30-36.

3. The method for preparing a moisture-resistant and mildew-resistant wall cloth coating according to claim 1, characterized in that: The isocyanate in step one is isophorone diisocyanate, and the molecular weight of the polyether polyol is 3000 and the functionality is 2.

4. The method for preparing a moisture-resistant and mildew-resistant wall cloth coating according to claim 1, characterized in that: The reaction monomer in step two is obtained by mixing ethyl methacrylate, methacrylic acid and isobornyl acrylate in a mass ratio of 10-12:3.0-4.2:1.0-1.

3.

5. The method for preparing a moisture-resistant and mildew-resistant wall cloth coating according to claim 1, characterized in that: The mass ratio of the antibacterial agent, the prepolymer, the reaction monomer, the photoinitiator and the auxiliary agent in step two is 8-10:45-55:100-110:2.5-3.0:2-3.

6. The method for preparing a moisture-resistant and mildew-resistant wall cloth coating according to claim 1, characterized in that: The mass ratio of the antibacterial filler, anhydrous ethanol and silane coupling agent in step A1 is 11-13:40-50:4.0-5.2, the antibacterial filler is a mixture of nano-silver and zinc oxide in a mass ratio of 5:1, and the silane coupling agent is vinyltriethoxysilane.

7. The method for preparing a moisture-resistant and mildew-resistant wall cloth coating according to claim 1, characterized in that: The composite monomer in step A2 is obtained by mixing methacrylic acid, cinnamic acid and hydroxyethyl methacrylic acid phosphate in a mass ratio of 6-8:2-3:1.0-1.

4.

8. The method for preparing a moisture-resistant and mildew-resistant wall cloth coating according to claim 1, characterized in that: The mass ratio of the intermediate material, anhydrous ethanol, composite monomer and initiator in step A2 is 8-10:20-30:2.0-2.4:0.06-0.

08.

9. A moisture-resistant and mildew-proof wall cloth coating prepared by the preparation method of any one of claims 1-8.

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