Antibacterial self-cleaning coating and preparation method thereof

Abstract

The invention discloses an antibacterial self-cleaning coating and a preparation method thereof, and relates to the technical field of coatings. The coating comprises a component A and a component B, the component A comprises the following components in parts by weight: 30-50 parts of modified epoxy resin, 10-15 parts of a solvent, 8-12 parts of nano zinc oxide and 0.5-1.2 parts of ammonium persulfate, and the component B comprises the following components in parts by weight: 5-10 parts of modified zinc oxide and 5-10 parts of 4, 4 '-diaminodicyclohexylmethane. The coating can present a micro-nano structure surface after being cured, the hydrophilicity of the coating is reduced, the self-cleaning effect of the coating is improved in cooperation with the photocatalytic effect, and meanwhile, the epoxy resin carries antibacterial groups and hydrophobic long chains, so that the antibacterial and self-cleaning effects of the coating can be further improved.

Description

Technical Field

[0001] The invention relates to the technical field of coatings, in particular to an antibacterial self-cleaning coating and a preparation method thereof. Background Art

[0002] Paints are mainly used to beautify the appearance and prevent corrosion. Commonly used paints are mainly organic solvent paints, which do not have hydrophobic properties. Traditional paints generally use epoxy resins, polyurethane resins, polyester resins or alkyd resins as polymer matrices, and use the high molecular weight of polymers to protect the substrate. Fillers such as graphite powder, titanium dioxide, and iron oxide are added to play a pigment and protective role. For some substrates used outdoors, such as building surfaces, fences, fences, isolation belts, etc., they are in a dusty and polluted environment and are very easy to get dirty. Cleaning them will waste a lot of resources and manpower.

[0003] With the gradual improvement of people's environmental awareness and social environmental protection needs, a series of products in the chemical industry in the past are facing replacement due to raw materials and additives that are not friendly to the human body and the environment, poor performance, etc. And with the gradual improvement of people's living standards, people pay more and more attention to health issues, but we are inevitably exposed to various bacteria and viruses in our daily lives. Some bacteria or viruses can become pathogens, causing human infection and causing serious harm to health. In order to solve such problems and improve the quality of life, we urgently need to apply green products with excellent physical properties and sterilization functions to life. Summary of the invention

[0004] The purpose of the present invention is to provide an antibacterial self-cleaning coating and a preparation method thereof to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: an antibacterial self-cleaning coating, comprising component A and component B, wherein component A comprises 30 to 50 parts by weight of modified epoxy resin, 10 to 15 parts of solvent, 8 to 12 parts of nano zinc oxide, and 0.5 to 1.2 parts of ammonium persulfate, and component B comprises 5 to 10 parts by weight of modified zinc oxide and 5 to 10 parts of 4,4′-diaminodicyclohexylmethane.

[0006] Furthermore, the solvent is xylene.

[0007] Furthermore, the particle size of the zinc oxide is 60 to 80 nm.

[0008] Furthermore, the preparation method of the modified zinc oxide is: add the modifier to distilled water and mix, then add it to anhydrous ethanol to prepare a solution with a modifier mass fraction of 3.5%, wherein the volume ratio of distilled water to anhydrous ethanol is 1:3, let it stand for 2 hours, then add zinc oxide with a particle size of 1 to 15 μm, ultrasonically disperse for 2 hours, then adjust the pH to 3.5 with glacial acetic acid, stir at a speed of 1500 r / min for 2 hours, and then vacuum dry to obtain the modified zinc oxide.

[0009] Furthermore, the mass ratio of vinyl triethoxysilane to KH-550 in the modifier is 1-5:1-5.

[0010] Furthermore, the mass ratio of the zinc oxide to the modifier is 0.5 to 3:1.

[0011] Furthermore, the modified epoxy resin comprises the following preparation steps:

[0012] (1) (3-trimethoxysilylpropyl) tri-n-butylammonium bromide, vinyl triethoxysilane, deionized water and anhydrous oxalic acid are mixed, stirred, and the speed is set to 250 r / min. The mixture is reacted at 50° C. for 3 to 6 hours under a nitrogen atmosphere, and then dimethyldimethoxysilane and dibutyltin dilaurate are added. The mixture is heated to 90° C. and refluxed for 3 to 6 hours. The reflux device is removed and the reaction is continued for 1 to 2 hours. The reactive silicone resin is then obtained after rotary evaporation at 60° C. for 30 minutes.

[0013] (2) After mixing the reactive silicone resin and the epoxy resin, xylene is added, and the mixture is reacted at 110 to 130° C. for 1 to 4 hours, and then the xylene is removed by distillation under reduced pressure to obtain a modified epoxy resin.

[0014] Furthermore, the mass ratio of (3-trimethoxysilylpropyl)tri-n-butylammonium bromide, vinyltriethoxysilane, deionized water, anhydrous oxalic acid, dimethyldimethoxysilane and dibutyltin dilaurate in step (1) is 60-100:150-200:22-30:0.2-1.0:50-70:1-3.

[0015] Furthermore, in step (2), the mass ratio of the reactive silicone resin to the epoxy resin is 1-4:5-10.

[0016] Furthermore, the epoxy resin in step (2) is bisphenol A epoxy resin.

[0017] Furthermore, in step (2), the mass ratio of the epoxy resin to xylene is 40:5.

[0018] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0019] (1) The present invention uses titanium dioxide and zinc oxide with photocatalytic effects as fillers in the coating, which improves the photocatalytic properties and antibacterial properties of the coating, and helps to improve the self-cleaning effect of the coating. Titanium dioxide and zinc oxide are mixed in the filler with nanoparticle sizes and micron particle sizes, respectively, and the ratio of the two is regulated so that the coating can present a micro-nanostructure surface after curing, reduce the hydrophilicity of the coating, and synergistically improve the self-cleaning effect of the coating with the photocatalytic effect;

[0020] (2) In order to achieve the dispersibility of micron-sized zinc oxide in the coating, vinyl triethoxysilane and KH-550 are used to mix and modify its surface, so that the surface has double bonds and amino groups at the same time, which can promote its dispersion effect and act as a co-curing agent to participate in the curing reaction of the modified epoxy resin. At the same time, the double bonds on the surface participate in the polymerization of double bonds in the coating components to form a double cross-linked network structure, so that the coating of the present invention can form a dense coating structure after curing, reduce the hydrophilicity of the coating, reduce the contact penetration of microorganisms, and improve the self-cleaning and antibacterial effects of the coating;

[0021] (3) The present invention uses (3-trimethoxysilylpropyl) tri-n-butylammonium bromide, vinyl triethoxysilane, and dimethyldimethoxysilane to generate a reactive silicone resin. At high temperature, the active methoxy groups on the reactive silicone resin molecules react with the hydroxyl groups on the main chain of the bisphenol A epoxy resin to introduce quaternary ammonium groups, thereby improving the antibacterial properties of the coating. The reactive silicone resin is combined with titanium dioxide and zinc oxide to achieve an organic-inorganic dual antibacterial effect. In addition, a silicon-oxygen segment is introduced into the side chain of the epoxy resin molecule to improve the hydrophobic effect of the epoxy resin and the self-cleaning effect of the coating. DETAILED DESCRIPTION

[0022] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] Example 1

[0024] An antibacterial self-cleaning coating comprises a component A and a component B, wherein the component A comprises, by weight, 30 parts of a modified epoxy resin, 10 parts of xylene, 8 parts of zinc oxide having a particle size of 60 nm, and 0.5 parts of ammonium persulfate, and the component B comprises, by weight, 5 parts of modified zinc oxide and 5 parts of 4,4′-diaminodicyclohexylmethane;

[0025] The preparation method of the modified zinc oxide is as follows: a modifier is added to distilled water and mixed, and then added to anhydrous ethanol to prepare a solution with a mass fraction of the modifier of 3.5%, wherein the mass ratio of vinyl triethoxysilane and KH-550 in the modifier is 1:1, and the volume ratio of distilled water to anhydrous ethanol is 1:3, and the solution is allowed to stand for 2 hours, and then zinc oxide with a particle size of 1 μm is added, ultrasonically dispersed for 2 hours, and then glacial acetic acid is used to adjust the pH to 3.5, and the solution is stirred at a speed of 1500 r / min for 2 hours, and then vacuum dried to obtain the modified zinc oxide; the mass ratio of the zinc oxide to the modifier is 1:1;

[0026] The modified epoxy resin comprises the following preparation steps:

[0027] (1) (3-trimethoxysilylpropyl) tri-n-butylammonium bromide, vinyl triethoxysilane, deionized water and anhydrous oxalic acid were mixed, stirred, and the speed was set to 250 r / min. The mixture was reacted at 50° C. for 5 h under a nitrogen atmosphere. Dimethyldimethoxysilane and dibutyltin dilaurate were then added, the temperature was raised to 90° C., and the mixture was refluxed for 5 h. The reflux device was removed and the reaction was continued for 1 h. The mixture was then rotary evaporated at 60° C. for 30 min to obtain a reactive silicone resin. The mass ratio of (3-trimethoxysilylpropyl) tri-n-butylammonium bromide, vinyl triethoxysilane, deionized water, anhydrous oxalic acid, dimethyldimethoxysilane and dibutyltin dilaurate was 60:150:22:0.2:50:1.

[0028] (2) After mixing reactive silicone resin and bisphenol A epoxy resin in a mass ratio of 1:5, xylene is added, reacting at 130° C. for 1 hour, and then distilling off the xylene under reduced pressure to obtain a modified epoxy resin; the mass ratio of the epoxy resin to the xylene is 40:5.

[0029] Example 2

[0030] An antibacterial self-cleaning coating comprises a component A and a component B, wherein the component A comprises, by weight, 35 parts of a modified epoxy resin, 12 parts of xylene, 8 parts of zinc oxide having a particle size of 60 nm, and 0.5 parts of ammonium persulfate, and the component B comprises, by weight, 10 parts of modified zinc oxide and 5 parts of 4,4′-diaminodicyclohexylmethane;

[0031] The preparation method of the modified zinc oxide is as follows: a modifier is added to distilled water and mixed, and then added to anhydrous ethanol to prepare a solution with a mass fraction of the modifier of 3.5%, wherein the mass ratio of vinyl triethoxysilane and KH-550 in the modifier is 1:3, and the volume ratio of distilled water to anhydrous ethanol is 1:3, and the solution is allowed to stand for 2 hours, and then zinc oxide with a particle size of 1 to 15 μm is added, ultrasonically dispersed for 2 hours, and then glacial acetic acid is used to adjust the pH to 3.5, and the solution is stirred at a speed of 1500 r / min for 2 hours, and then vacuum dried to obtain the modified zinc oxide; the mass ratio of the zinc oxide to the modifier is 1.4:1;

[0032] The modified epoxy resin comprises the following preparation steps:

[0033] (1) (3-trimethoxysilylpropyl) tri-n-butylammonium bromide, vinyl triethoxysilane, deionized water and anhydrous oxalic acid were mixed, stirred, and the speed was set to 250 r / min. The mixture was reacted at 50° C. for 6 h under a nitrogen atmosphere. Dimethyldimethoxysilane and dibutyltin dilaurate were then added, the temperature was raised to 90° C., and the mixture was refluxed for 6 h. The reflux device was removed and the reaction was continued for 1 h. The mixture was then rotary evaporated at 60° C. for 30 min to obtain a reactive silicone resin. The mass ratio of (3-trimethoxysilylpropyl) tri-n-butylammonium bromide, vinyl triethoxysilane, deionized water, anhydrous oxalic acid, dimethyldimethoxysilane and dibutyltin dilaurate was 70:170:24:0.4:55:1.

[0034] (2) After mixing reactive silicone resin and bisphenol A epoxy resin in a mass ratio of 1:9, xylene is added, reacted at 130° C. for 2 hours, and then xylene is removed by reduced pressure distillation to obtain a modified epoxy resin; the mass ratio of epoxy resin to xylene is 40:5.

[0035] Example 3

[0036] An antibacterial self-cleaning coating comprises a component A and a component B, wherein the component A comprises, by weight, 40 parts of a modified epoxy resin, 12 parts of xylene, 10 parts of zinc oxide having a particle size of 70 nm, and 1 part of ammonium persulfate, and the component B comprises, by weight, 8 parts of modified zinc oxide and 6 parts of 4,4′-diaminodicyclohexylmethane;

[0037] The preparation method of the modified zinc oxide is as follows: a modifier is added into distilled water and mixed, and then added into anhydrous ethanol to prepare a solution with a mass fraction of the modifier of 3.5%, wherein the mass ratio of vinyl triethoxysilane and KH-550 in the modifier is 2:4, and the volume ratio of distilled water to anhydrous ethanol is 1:3, and the solution is allowed to stand for 2 hours, and then zinc oxide with a particle size of 8 μm is added, ultrasonically dispersed for 2 hours, and then glacial acetic acid is used to adjust the pH to 3.5, and the solution is stirred at a speed of 1500 r / min for 2 hours, and then vacuum dried to obtain the modified zinc oxide; the mass ratio of the zinc oxide to the modifier is 2:1;

[0038] The modified epoxy resin comprises the following preparation steps:

[0039] (1) (3-trimethoxysilylpropyl) tri-n-butylammonium bromide, vinyl triethoxysilane, deionized water and anhydrous oxalic acid were mixed, stirred, and the speed was set to 250 r / min. The mixture was reacted at 50° C. for 4 h under a nitrogen atmosphere. Dimethyldimethoxysilane and dibutyltin dilaurate were then added, the temperature was raised to 90° C., and the mixture was refluxed for 4 h. The reflux device was removed and the reaction was continued for 1 h. The mixture was then rotary evaporated at 60° C. for 30 min to obtain a reactive silicone resin. The mass ratio of (3-trimethoxysilylpropyl) tri-n-butylammonium bromide, vinyl triethoxysilane, deionized water, anhydrous oxalic acid, dimethyldimethoxysilane and dibutyltin dilaurate was 86:186:27:0.4:65:1.5.

[0040] (2) After mixing reactive silicone resin and bisphenol A epoxy resin in a mass ratio of 2:8, xylene is added, reacted at 130° C. for 4 hours, and then xylene is removed by reduced pressure distillation to obtain a modified epoxy resin; the mass ratio of epoxy resin to xylene is 40:5.

[0041] Example 4

[0042] An antibacterial self-cleaning coating comprises a component A and a component B, wherein the component A comprises, by weight, 50 parts of a modified epoxy resin, 15 parts of xylene, 12 parts of zinc oxide having a particle size of 80 nm, and 1.2 parts of ammonium persulfate, and the component B comprises, by weight, 10 parts of modified zinc oxide and 10 parts of 4,4′-diaminodicyclohexylmethane;

[0043] The preparation method of the modified zinc oxide is as follows: a modifier is added to distilled water and mixed, and then added to anhydrous ethanol to prepare a solution with a mass fraction of the modifier of 3.5%, wherein the mass ratio of vinyl triethoxysilane and KH-550 in the modifier is 5:2, and the volume ratio of distilled water to anhydrous ethanol is 1:3, and the solution is allowed to stand for 2 hours, and then zinc oxide with a particle size of 15 μm is added, ultrasonically dispersed for 2 hours, and then glacial acetic acid is used to adjust the pH to 3.5, and the solution is stirred at a speed of 1500 r / min for 2 hours, and then vacuum dried to obtain the modified zinc oxide; the mass ratio of the zinc oxide to the modifier is 3:1;

[0044] The modified epoxy resin comprises the following preparation steps:

[0045] (1) (3-trimethoxysilylpropyl) tri-n-butylammonium bromide, vinyl triethoxysilane, deionized water and anhydrous oxalic acid were mixed, stirred, and the speed was set to 250 r / min. The mixture was reacted at 50° C. for 6 h under a nitrogen atmosphere. Dimethyldimethoxysilane and dibutyltin dilaurate were then added, the temperature was raised to 90° C., and the mixture was refluxed for 6 h. The reflux device was removed and the reaction was continued for 2 h. The mixture was then rotary evaporated at 60° C. for 30 min to obtain a reactive silicone resin. The mass ratio of (3-trimethoxysilylpropyl) tri-n-butylammonium bromide, vinyl triethoxysilane, deionized water, anhydrous oxalic acid, dimethyldimethoxysilane and dibutyltin dilaurate was 100:198:28:0.5:70:2.5.

[0046] (2) After mixing reactive silicone resin and bisphenol A epoxy resin in a mass ratio of 3:7, xylene is added, reacting at 130° C. for 4 hours, and then distilling off the xylene under reduced pressure to obtain a modified epoxy resin; the mass ratio of the epoxy resin to the xylene is 40:5.

[0047] Comparative Example 1

[0048] The difference between Comparative Example 1 and Example 1 is that titanium dioxide is not added, and the remaining steps and components are the same as Example 1.

[0049] Comparative Example 2

[0050] The difference between Comparative Example 2 and Example 1 is that zinc oxide is not added, and the remaining steps and components are the same as Example 1.

[0051] Comparative Example 3

[0052] The difference between Comparative Example 3 and Example 1 is that the surface of zinc oxide is only modified by vinyltriethoxysilane, and the remaining steps and components are the same as Example 1.

[0053] Comparative Example 4

[0054] The difference between Comparative Example 4 and Example 1 is that the surface of zinc oxide is only modified by KH-550, and the remaining steps and components are the same as Example 1.

[0055] Comparative Example 5

[0056] The difference between Comparative Example 5 and Example 1 is that (3-trimethoxysilylpropyl)tri-n-butylammonium bromide is not added to participate in the polymerization of the reactive silicone resin, and the remaining steps and components are the same as Example 1.

[0057] Comparative Example 6

[0058] The difference between Comparative Example 6 and Example 1 is that no vinyltriethoxysilane is added to participate in the polymerization of the reactive silicone resin, and the remaining steps and components are the same as Example 1.

[0059] Comparative Example 7

[0060] The difference between Comparative Example 7 and Example 1 is that no reactive silicone resin is generated, and the remaining steps and components are the same as Example 1.

[0061] Comparative Example 8

[0062] The difference between Comparative Example 8 and Example 1 is that the particle sizes of zinc oxide and titanium dioxide are the same, and the remaining steps and components are the same as Example 1.

[0063] Effect example

[0064] Table 1 below shows the coatings prepared by Examples 1 to 4 of the present invention and Comparative Examples 1 to 8 were mixed according to the component ratio, fully stirred for 10 minutes, coated on the polished tinplate, and cured in a high-temperature oven at 80° C. for 8 hours, then heated to 120° C. for 1 hour, and the performance analysis results of various properties of the obtained coatings were performed.

[0065] Table 1

[0066]

[0067] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. An antibacterial self-cleaning coating, comprising component A and component B, characterized in that: The component A comprises 30-50 parts of modified epoxy resin, 10-15 parts of solvent, 8-12 parts of nano zinc oxide, and 0.5-1.2 parts of ammonium persulfate by weight, and the component B comprises 5-10 parts of modified zinc oxide and 5-10 parts of 4,4'-diaminodicyclohexylmethane by weight.

2. The antibacterial self-cleaning coating according to claim 1, characterized in that: The solvent is xylene.

3. The antibacterial self-cleaning coating according to claim 1, characterized in that: The particle size of the zinc oxide is 60-80 nm.

4. The antibacterial self-cleaning coating according to claim 1, characterized in that: The modified zinc oxide is zinc oxide with a particle size of 1 to 15 μm, and the surface of the zinc oxide is modified by vinyl triethoxysilane and KH-550.

5. The antibacterial self-cleaning coating according to claim 1, characterized in that: The modified epoxy resin comprises the following preparation steps: (1) (3-trimethoxysilylpropyl) tri-n-butylammonium bromide, vinyl triethoxysilane, deionized water and anhydrous oxalic acid are mixed, stirred, and the speed is set to 250 r / min. The mixture is reacted at 50° C. for 3 to 6 hours under a nitrogen atmosphere, and then dimethyldimethoxysilane and dibutyltin dilaurate are added. The mixture is heated to 90° C. and refluxed for 3 to 6 hours. The reflux device is removed and the reaction is continued for 1 to 2 hours. The reactive silicone resin is then obtained after rotary evaporation at 60° C. for 30 minutes. (2) After mixing the reactive silicone resin and the epoxy resin, xylene is added, and the mixture is reacted at 110 to 130° C. for 1 to 4 hours, and then the xylene is removed by distillation under reduced pressure to obtain a modified epoxy resin.

6. The antibacterial self-cleaning coating according to claim 5, characterized in that: The mass ratio of (3-trimethoxysilylpropyl)tri-n-butylammonium bromide, vinyltriethoxysilane, deionized water, anhydrous oxalic acid, dimethyldimethoxysilane and dibutyltin dilaurate in step (1) is 60-100:150-200:22-30:0.2-1.0:50-70:1-3.

7. The antibacterial self-cleaning coating according to claim 5, characterized in that: In step (2), the mass ratio of the reactive silicone resin to the epoxy resin is 1-4:5-10.

8. The antibacterial self-cleaning coating according to claim 5, characterized in that: The epoxy resin in step (2) is bisphenol A type epoxy resin.

9. The antibacterial self-cleaning coating according to claim 5, characterized in that: The mass ratio of the epoxy resin to xylene in step (2) is 40:5.

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