CN114058220A - Antibacterial and mildewproof coating and preparation method and application thereof - Google Patents
Antibacterial and mildewproof coating and preparation method and application thereof Download PDFInfo
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- CN114058220A CN114058220A CN202111676287.6A CN202111676287A CN114058220A CN 114058220 A CN114058220 A CN 114058220A CN 202111676287 A CN202111676287 A CN 202111676287A CN 114058220 A CN114058220 A CN 114058220A
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09D109/06—Copolymers with styrene
- C09D109/08—Latex
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Abstract
The invention relates to an antibacterial and mildewproof coating and a preparation method and application thereof. The antibacterial and mildewproof coating comprises emulsion and modified nano-alumina; the mass ratio of the emulsion to the modified nano-alumina is (50-1200): 1; the preparation method of the modified nano-alumina comprises the following steps: mixing the raw materials for preparing the modified nano-alumina, and carrying out ball milling treatment; the raw materials comprise nano aluminum oxide, a modifier and a dispersant; the modifier is selected from one or more of ascorbic acid, L-cysteine, L-arginine or L-alanine. The antibacterial and mildewproof coating based on the nano aluminum oxide has the advantages of excellent antibacterial and mildewproof effect, low toxicity, difficulty in causing bacterial drug resistance, simple preparation method, low cost, simple use method and wide application prospect.
Description
Technical Field
The invention relates to the technical field of functional coatings, in particular to an antibacterial and mildewproof coating and application thereof.
Background
Bacteria are everywhere and can multiply on the surfaces of various objects which are contacted with the bacteria in daily life, especially in some public places. Therefore, the use of biocides and the construction of self-disinfecting surfaces are considered the most effective solutions to the problem and have received widespread attention. Moreover, the requirements for antibacterial performance in materials such as home decoration, automobile interior decoration, marine corrosion prevention, industrial corrosion prevention and the like are more and more strict.
Coatings have become unavoidable materials to be contacted in human daily life, and the antibacterial performance of the coatings is receiving more and more attention. In addition, the paint is extremely easy to mildew in places with little or no direct sunlight, especially in humid areas, once the paint is affected with damp, the mildew is easy to breed, and the phenomena of peeling and falling off of the wall paint can be seriously caused. The development of the antibacterial coating which can effectively inhibit bacteria and prevent mildew without inducing radiation is particularly urgent.
At present, most of coatings use organic antibacterial agents to enhance the antibacterial performance of the coatings, and due to the problems of poor durability, high toxicity and the like of the organic antibacterial agents, more and more research and development workers turn the research and development of antibacterial coatings to the direction of nano antibacterial materials. The wide use of traditional fungicides has developed resistance, while nanomaterials do not generally develop resistance, which makes them a significant advantage over traditional fungicides. Further, the nano material easily penetrates the bacterial cell membrane, thereby having more excellent antibacterial performance.
Nano alumina (Al)2O3) The nano-alumina is a common industrial catalyst, has the advantages of low toxicity, low price, stability and the like, and has wide application field, but the unmodified nano-alumina has poor antibacterial activity, and the nano-alumina has large specific surface area, high surface energy in a thermodynamic unstable state, is very easy to aggregate and has poor dispersibility.
Similarly, most of the existing coatings use organic mildew inhibitors to enhance the mildew resistance, mainly comprise phenolic compounds (substituted aromatic hydrocarbons), element organic compounds, nitrogen-containing organic compounds, halogen-containing organic compounds, sulfur-containing organic compounds and the like, and the organic mildew inhibitors have high toxicity and are not environment-friendly.
In conclusion, the organic antibacterial agent and the organic mildew preventive are added into the paint at the same time, so that the toxicity of the paint is undoubtedly greatly increased, and how to replace the organic antibacterial agent and the organic mildew preventive with inorganic matters to reduce the toxicity has important significance.
Disclosure of Invention
Aiming at the problems, the invention provides the antibacterial and mildewproof coating which has excellent antibacterial and mildewproof effects, low toxicity and difficult induction of bacterial drug resistance.
The technical scheme is as follows:
an antibacterial and mildewproof coating comprises emulsion and modified nano-alumina;
the mass ratio of the emulsion to the modified nano-alumina is (50-1200): 1;
the preparation method of the modified nano-alumina comprises the following steps:
mixing the raw materials for preparing the modified nano-alumina, and carrying out ball milling treatment;
the raw materials comprise nano aluminum oxide, a modifier and a dispersant;
the modifier is selected from one or more of ascorbic acid, L-cysteine, L-arginine or L-alanine.
In one embodiment, the emulsion is a styrene-butadiene emulsion, a vinyl acetate emulsion, a polyvinylidene chloride emulsion, or a polysulfide-vinylidene chloride emulsion.
In one embodiment, the mass ratio of the emulsion to the modified nano aluminum oxide is (50-600): 1.
in one embodiment, the mass ratio of the nano alumina to the modifier is (1-8): 1.
in one embodiment, the mass ratio of the nano alumina to the water is 1: (100-1000).
In one embodiment, the ball milling medium used in the ball milling process is zirconia beads with a particle size of 0.05mm to 0.5 mm.
In one embodiment, the mass ratio of the nano alumina to the ball milling medium is 1: (50-1000).
In one embodiment, the temperature of the ball milling treatment is 20-40 ℃, the rotating speed of the ball milling treatment is 200-500 rpm, and the time is 1-5 h.
In one embodiment, the nano alumina has a particle size of 2000nm to 8000 nm.
In one embodiment, the purity of the nano alumina is more than or equal to 99.99%.
In one embodiment, the modifier has a purity of BR grade.
In one embodiment, the raw material for preparing the modified nano alumina further comprises a surfactant.
In one embodiment, the surfactant is selected from one or more of sodium dodecyl benzene sulfonate (SDS), sodium laurate, a silane coupling agent, and tween 80.
In one embodiment, the mass ratio of the nano aluminum oxide to the surfactant is (1-10): 1.
the invention also provides a preparation method of the antibacterial and mildewproof coating, which comprises the following steps:
mixing the emulsion and the modified nano-alumina.
In one embodiment, the manner of mixing the emulsion and the modified nano-alumina is mechanical stirring, and the rotating speed is 500rpm to 1500 rpm.
The invention also provides an architectural coating, which comprises the antibacterial and mildewproof coating.
The invention also provides a furniture coating which comprises the antibacterial and mildewproof coating.
The invention has the following beneficial effects:
the antibacterial mildew-proof coating provided by the invention comprises emulsion and modified nano-alumina, wherein the preparation method of the modified nano-alumina comprises the steps of mixing the nano-alumina, a specific modifier and water, and carrying out ball milling treatment. The nano-alumina is safe and low in toxicity, and does not cause the problem of drug resistance, active sites are collided on the surface of the nano-alumina through ball milling, the modifier is grafted on the nano-alumina through the active sites, and the nano-alumina is subjected to mechanical (ball milling) -chemical modification through the method, so that the dispersing performance of the nano-alumina is obviously improved, the nano-alumina is favorably and uniformly dispersed in emulsion, and the antibacterial property, the mildew resistance and the stability of the nano-alumina are further improved. Meanwhile, the modified nano-alumina also has excellent drying property and chemical stability, so that the coating is dehumidified in a humid and dark environment, can keep dry and stable for a long time, and further enhances the antibacterial and mildew-proof properties of the coating. In addition, researches show that the antibacterial and mildew-proof performance of the coating can be met by adding a small amount of modified nano-alumina, so that the luster, the color and the like of the coating cannot be obviously influenced, and the modified nano-alumina has multiple adaptation types to the coating and wide application fields.
Tests prove that the antibacterial and mildewproof coating based on the nano aluminum oxide has the bacteriostatic rate of 99.76 percent on staphylococcus aureus and 99.54 percent on escherichia coli, has excellent antibacterial property, the bacteriostatic rate of 0 grade on candida albicans, has excellent mildewproof property and can durably resist bacteria and mildewproof.
The antibacterial and mildew-proof coating based on the nano-alumina can be prepared by blending, the preparation method is simple to operate, does not need complex equipment, is low in cost, is environment-friendly and pollution-free, does not cause obvious influence on the production of the coating, and can be industrially produced in an enlarged manner.
Drawings
FIG. 1a is a picture of a coating layer formed by the coating material of comparative example 1, and FIG. 1b is a picture of a coating layer formed by the nano alumina-based antibacterial and antifungal coating material prepared in example 1;
FIG. 2a is a photograph of a culture medium of the coating of comparative example 1 after 24 hours of incubation with a bacterial solution, and FIG. 2b is a photograph of a culture medium of the antibacterial and antifungal coating based on nano-alumina prepared in example 1 after 24 hours of incubation with a bacterial solution.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Where the terms "comprising," "having," and "including" are used herein, it is intended to cover a non-exclusive inclusion, as another element may be added, unless an explicit limitation is used, such as "only," "consisting of … …," etc.
The words "preferably," "more preferably," and the like, in the present disclosure mean embodiments of the disclosure that may, in some instances, provide certain benefits. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
Unless mentioned to the contrary, terms in the singular may include the plural and are not to be construed as being one in number.
The antibacterial and mildewproof coating provided by the invention has the advantages of excellent antibacterial and mildewproof effect, low toxicity and difficulty in causing bacterial drug resistance.
The technical scheme is as follows:
an antibacterial and mildewproof coating comprises emulsion and modified nano-alumina;
the mass ratio of the emulsion to the modified nano-alumina is (50-1200): 1;
the preparation method of the modified nano-alumina comprises the following steps:
mixing the raw materials for preparing the modified nano-alumina, and carrying out ball milling treatment;
the raw materials comprise nano aluminum oxide, a modifier and a dispersant;
the modifier is selected from one or more of ascorbic acid, L-cysteine, L-arginine or L-alanine.
The nano-alumina is safe and low in toxicity, and does not cause the problem of drug resistance, active sites are collided on the surface of the nano-alumina through ball milling, a specific modifier is grafted on the nano-alumina through the active sites, and the nano-alumina is subjected to mechanical (ball milling) -chemical modification through the method, so that the dispersing performance of the nano-alumina is obviously improved, the nano-alumina is favorably and uniformly dispersed in emulsion, and the antibacterial property, the mildew resistance and the stability of the nano-alumina are further improved. Meanwhile, the modified nano-alumina also has excellent drying property and chemical stability, so that the coating is dehumidified in a humid and dark environment, can keep dry and stable for a long time, and further enhances the antibacterial and mildew-proof properties of the coating. In addition, researches show that the antibacterial and mildew-proof performance of the coating can be met by adding a small amount of modified nano-alumina, so that the luster, the color and the like of the coating cannot be obviously influenced, and the modified nano-alumina has multiple adaptation types to the coating and wide application fields. In addition, the method for modifying the nano-alumina has the advantages of simple process, simple and convenient operation, high production efficiency, time and energy conservation, production cost reduction and suitability for industrial production.
It is appreciated that the antibacterial and mildew-proof performance of the coating can be satisfied by adding a small amount of the modified nano-alumina of the invention into the emulsion, so that the luster, the color and the like of the coating cannot be obviously influenced, and the modified nano-alumina has a plurality of adaptation types to the coating and has wide application fields.
In one embodiment, the emulsion is a styrene-butadiene emulsion, a vinyl acetate emulsion, a polyvinylidene chloride emulsion, or a polysulfide-vinylidene chloride emulsion.
In the invention, the mass ratio of the emulsion to the modified nano-alumina is (50-1200): 1, including but not limited to: 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, 110:1, 120:1, 130:1, 140:1, 150:1, 160:1, 170:1, 180:1, 190:1, 200: 1. 210:1, 220:1, 230:1, 240:1, 250:1, 260:1, 270:1, 280:1, 290:1, 300:1, 310:1, 320:1, 330:1, 340:1, 350:1, 360:1, 370:1, 380:1, 390:1, 400:1, 410:1, 420:1, 430:1, 440:1, 450:1, 460:1, 470:1, 480:1, 490:1, 500:1, 510:1, 520:1, 530:1, 540:1, 550:1, 560:1, 570:1, 580:1, 590:1, 600:1, 620:1, 650:1, 680:1, 700:1, 720:1, 750:1, 780:1, 800:1, 820:1, 850:1, 880:1, 900: 1. 920:1, 950:1, 980:1, 1000: 1. 1020:1, 1050:1, 1080:1, 1100: 1. 1120:1, 1150:1, 1180:1, and 1200: 1. preferably, the mass ratio of the emulsion to the modified nano-alumina is (50-600): 1. further preferably, the mass ratio of the emulsion to the modified nano-alumina is (50-300): 1.
in the invention, one or more of ascorbic acid, L-cysteine, L-arginine or L-alanine is used as a modifier to graft and modify the nano alumina, so that the dispersibility of the nano alumina can be improved, the modified nano alumina is endowed with excellent antibacterial and mildew-proof properties, and meanwhile, the compatibility between the nano alumina and a coating can be increased, so that the modified nano alumina is better filled in the coating to play an antibacterial and mildew-proof role.
In one preferred embodiment, the modifying agent is ascorbic acid, which has the functions of resisting oxidation, resisting free radicals and inhibiting the formation of tyrosinase.
In another preferred embodiment, the modifier is L-cysteine. The inventor researches and discovers that the hydrophilic group in the L-cysteine molecule can promote the nano-alumina to be more hydrophilic and more easily dispersed in the water phase, and the sulfydryl on the surface of the L-cysteine molecule can form certain electrostatic repulsion to prevent the nano-particles from agglomerating so as to promote the nano-particles to form monodisperse and uniform colloid. In addition, the inventor also finds that the yield of the L-cysteine grafted nano alumina aqueous colloidal solution obtained by the ball milling method in the invention is as high as more than 90%.
In one embodiment, the modifier has a purity of BR grade.
In one embodiment, the nano alumina has a particle size of 2000nm to 8000 nm.
In one embodiment, the purity of the nano alumina is more than or equal to 99.99%.
In one embodiment, the mass ratio of the nano alumina to the modifier is (1-8): 1, including but not limited to: 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1 and 8: 1. the inventor researches and discovers that the antibacterial and mildewproof performance of the modified nano-alumina is related to the content of the modifier, the higher the grafting ratio of the modifier is, the stronger the antibacterial performance and the mildewproof performance are, but if the grafting ratio exceeds the range, the grafting ratio is reduced. Preferably, the mass ratio of the nano aluminum oxide to the modifier is (1-5): 1.
in one embodiment, the mass ratio of the nano alumina to the water is 1: (100-1000) including, but not limited to: 1: 100. 1: 110. 1: 120. 1: 130. 1: 140. 1: 150. 1: 160. 1: 170. 1: 180. 1: 190. 1: 200. 1: 210. 1: 220. 1: 230. 1: 240. 1: 250. 1: 260. 1: 270. 1: 280. 1: 290. 1: 300. 1: 310. 1: 320. 1: 330. 1: 340. 1: 350. 1: 360. 1: 370. 1: 380. 1: 390. 1: 400. 1: 420. 1: 450. 1: 480. 1: 500. 1: 520. 1: 550. 1: 580. 1:600, 1: 650. 1: 700. 1: 750. 1: 800. 1: 850. 1: 900. 1: 950 and 1: 1000. Preferably, the mass ratio of the nano alumina to the water is 1: (100-500). Further preferably, the mass ratio of the nano alumina to the water is 1: (100-200). Still further preferably, the mass ratio of the nano alumina to the water is 1: (100-150).
It is understood that the use of water as a ball milling dispersant is more economical and environmentally friendly. Further, the water is deionized water, and the pH value of the deionized water is 6.5-6.8.
In one embodiment, the modified nano alumina is colloidal or powdery. Preferably, the modified nano-alumina is in a colloid shape, so that the modified nano-alumina is conveniently and uniformly mixed with the emulsion, the uniformity of the antibacterial and mildewproof coating is improved, and the antibacterial property and the mildewproof property of the antibacterial and mildewproof coating are further improved.
It will be appreciated that the ball milling process may be carried out in a planetary ball mill. And after the ball milling is finished, standing for 10-30 min, taking out the ball milling tank, removing the ball milling medium, and preparing the colloidal modified nano aluminum oxide. Further, the colloidal modified nano alumina is dried to obtain a powdery modified nano alumina.
In one embodiment, the ball milling media are zirconia beads having a particle size of 0.05mm to 0.5 mm. The inventor researches and discovers that the particle size of the ball milling medium can influence the dispersion state of the nano alumina in water, and the particle size of the ball milling medium is controlled, so that more uniform and transparent colloid can be obtained, and better antibacterial effect and mildew-proof effect can be obtained.
In one embodiment, the mass ratio of the nano alumina to the ball milling medium is 1: (50-1000) including, but not limited to: 1: 50. 1: 60. 1: 70. 1: 80. 1: 90. 1: 100. 1: 200. 1: 250. 1: 300. 1: 400. 1:500, 1: 500. 1: 550. 1: 600. 1: 700. 1: 800. 1: 900 and 1: 1000. preferably, the mass ratio of the nano alumina to the ball milling medium is 1: (50-600). Further preferably, the mass ratio of the nano alumina to the ball milling medium is 1: (50-200).
In one embodiment, the temperature of the ball milling process is 20 ℃ to 40 ℃, including but not limited to: 20 ℃, 22 ℃, 25 ℃, 30 ℃, 31 ℃, 32 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃ and 40 ℃.
In one embodiment, the rotation speed of the ball milling process is 200rpm to 500rpm, including but not limited to: 200rpm, 220rpm, 250rpm, 300rpm, 320rpm, 350rpm, 400rpm, 420rpm, 450rpm, and 500 rpm. The inventor researches and discovers that the ball milling rotating speed can influence the dispersion form of the nano aluminum oxide in water, and more uniform and transparent colloid can be obtained by controlling the ball milling rotating speed, so that better antibacterial effect and mildew-proof effect can be obtained.
In one embodiment, the ball milling time is 1-5 h. The inventor researches and discovers that the dispersion form of the nano zinc oxide in water can be influenced by the length of the ball milling time, and more uniform and transparent colloid and better antibacterial effect and mildew-proof effect can be obtained by controlling the ball milling time.
In one embodiment, the raw material for preparing the modified nano alumina further comprises a surfactant. The research of the inventor finds that the surfactant is additionally added to further promote the dispersion of the nano-alumina, further improve the agglomeration problem of the nano-alumina and improve the antibacterial effect and the mildew-proof effect.
In one embodiment, the surfactant is selected from one or more of sodium dodecyl benzene sulfonate (SDS), sodium laurate, and tween 80.
In one embodiment, the mass ratio of the nano aluminum oxide to the surfactant is (1-10): 1, including but not limited to: 1:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, and 10: 1.
The invention also provides a preparation method of the antibacterial and mildewproof coating based on the nano aluminum oxide, which comprises the following steps:
mixing the coating and the modified nano-alumina.
In one embodiment, the manner of mixing the coating and the modified nano alumina is mechanical stirring, and the rotating speed is 500rpm to 1500 rpm.
The invention also provides an architectural coating, which comprises the antibacterial and mildewproof coating based on the nano aluminum oxide. Preferably, the architectural coating is an interior wall coating.
The invention also provides a furniture coating which comprises the antibacterial and mildewproof coating based on the nano aluminum oxide.
In a preferred embodiment, the nano-alumina based antibacterial and mildewproof coating is sprayed by a common spray gun, is simple to operate and is also suitable for industrial spraying. Further, the curing conditions of the antibacterial and mildewproof coating based on the nano aluminum oxide are natural curing (according to the curing conditions of different commercially available styrene-butadiene emulsions), namely curing for 48 hours at room temperature after spraying, and then testing the performance of the antibacterial and mildewproof coating.
The present invention will be further described with reference to specific examples.
(1) The antibacterial performance test method of the coating comprises the following steps: the antibacterial and mildewproof coatings prepared in the following examples and comparative examples were uniformly sprayed on glass plates of 50 x 4mm, cured at room temperature for 48h, and tested for antibacterial performance according to standard HG/T3950-2007 appendix A. Testing strains: escherichia coli ATCC 25922, Staphylococcus aureus ATCC 29213 and Candida albicans CMCC 98001.
(2) The invention relates to a method for testing the mildew resistance of a coating, which comprises the following steps: and (3) performing a mildew resistance test on the coating according to a paint film mildew resistance test method of GB-T1741-2007. Testing strains: candida albicans CMCC 98001.
Example 1
The embodiment provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.5g of ascorbic acid, 0.25g of SDS powder and 50g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the ascorbic acid grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.6g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The coating formed by the coating without the modified nano alumina added in comparative example 1 was used as a blank and subjected to appearance analysis, the result of which is shown in fig. 1a, and the coating formed by the nano alumina-based antibacterial and antifungal coating prepared in this example was subjected to appearance analysis, the result of which is shown in fig. 1 b. Comparing fig. 1a and fig. 1b, it can be seen that the coating layer after adding the modified nano alumina and the coating layer without adding the modified nano alumina have no obvious difference in appearance, which indicates that the modified nano alumina of the present invention does not affect the original color of the coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared in the embodiment is uniformly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The coating formed by the coating without the added modified nano-alumina is used as a blank control, and the results are shown in figure 2a, and the coating formed by the nano-alumina-based antibacterial and mildewproof coating prepared in the embodiment is subjected to a mildewproof test according to GB-T1741-2007, and the results are shown in table 1 and figure 2 b. Comparing fig. 2a and fig. 2b, it can be seen that the surface of the coating sample plate without adding modified nano alumina in comparative example 1 is full of colonies after 24h of bacterial liquid culture, and no colonies are generated on the surface of the sample plate with adding nano alumina, which indicates that the coating with adding modified nano alumina has excellent mildew resistance.
Example 2
The embodiment provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.5g of ascorbic acid, 0.25g of SDS powder and 50g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the ascorbic acid grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.3g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared in the embodiment is uniformly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The antibacterial and mildewproof coating based on the nano alumina prepared in the embodiment is subjected to a mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Example 3
The embodiment provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.5g of ascorbic acid, 0.25g of SDS powder and 50g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the ascorbic acid grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.15g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared in the embodiment is uniformly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The antibacterial and mildewproof coating based on the nano alumina prepared in the embodiment is subjected to a mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Example 4
The embodiment provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.5g of ascorbic acid, 0.25g of SDS powder and 50g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the ascorbic acid grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.05g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared in the embodiment is uniformly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The antibacterial and mildewproof coating based on the nano alumina prepared in the embodiment is subjected to a mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Example 5
The embodiment provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.5g of ascorbic acid, 0.25g of SDS powder and 50g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the ascorbic acid grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.04g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared in the embodiment is uniformly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The antibacterial and mildewproof coating based on the nano alumina prepared in the embodiment is subjected to a mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Example 6
The embodiment provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.5g of ascorbic acid, 0.25g of SDS powder and 50g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 4h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the ascorbic acid grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.03g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared in the embodiment is uniformly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The anti-mildew coating based on nano alumina prepared in the embodiment is subjected to anti-mildew tests according to GB-T1741-2007, and the results are shown in a graph 1.
Example 7
The embodiment provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.5g L-arginine, 0.25g of SDS powder and 50g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the L-arginine grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.6g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared in the embodiment is uniformly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The antibacterial and mildewproof coating based on the nano alumina prepared in the embodiment is subjected to a mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Example 8
The embodiment provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.5g L-alanine, 0.25g of SDS powder and 50g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the L-alanine grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.6g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared in the embodiment is uniformly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The antibacterial and mildewproof coating based on the nano alumina prepared in the embodiment is subjected to a mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Example 9
The embodiment provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.5g L-cysteine, 0.25g of SDS powder and 50g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the L-cysteine grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.6g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared in the embodiment is uniformly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The antibacterial and mildewproof coating based on the nano alumina prepared in the embodiment is subjected to a mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Example 10
The embodiment provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling tank with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.25L-arginine, 0.25L-alanine, 0.25g of SDS powder and 50g of deionized water are weighed and put into the ball milling tank.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the L-arginine and L-alanine grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.6g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared in the embodiment is uniformly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The antibacterial and mildewproof coating based on the nano alumina prepared in the embodiment is subjected to a mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Example 11
The embodiment provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.25g of ascorbic acid, 0.25g of SDS powder and 50g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the ascorbic acid grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.6g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared in the embodiment is uniformly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The antibacterial and mildewproof coating based on the nano alumina prepared in the embodiment is subjected to a mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Example 12
The embodiment provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.08g of ascorbic acid, 0.25g of SDS powder and 50g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the ascorbic acid grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.6g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared in the embodiment is uniformly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The antibacterial and mildewproof coating based on the nano alumina prepared in the embodiment is subjected to a mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Example 13
The embodiment provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.5g of ascorbic acid, 0.25g of SDS powder and 100g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the ascorbic acid grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.6g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared in the embodiment is uniformly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The coating formed by the antibacterial and mildewproof coating based on the nano alumina prepared in the embodiment is subjected to a mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Example 14
The embodiment provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.5g of ascorbic acid, 025g of SDS powder and 200g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the ascorbic acid grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.6g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared in the embodiment is uniformly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The antibacterial and mildewproof coating based on the nano alumina prepared in the embodiment is subjected to a mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Example 15
The embodiment provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.08g of ascorbic acid, 005g of SDS powder and 500g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 400rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the ascorbic acid grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.6g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared in the embodiment is uniformly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The antibacterial and mildewproof coating based on the nano alumina prepared in the embodiment is subjected to a mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Comparative example 1
In comparison with example 1, the coating of this comparative example was subjected to appearance analysis without blending the modified nano alumina and the coating, using the coating formed with the coating to which the modified nano alumina was not added as a blank control, and the results are shown in fig. 1 a.
The coating of the comparative example was sprayed uniformly onto 50 x 4mm glass plates, cured at room temperature for 48h and tested for antibacterial activity according to standard HG/T3950-.
The coating formed with the coating without the addition of the modified nano alumina was subjected to a mildew resistance test using as a blank control, the results of which are shown in fig. 2a and table 1.
Comparative example 2
The comparative example provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.5g of protocatechuic acid, 0.25g of SDS powder and 50g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the mixed solution of protocatechuic acid and nano-alumina, and taking the mixed solution as the modified nano-alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.6g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared by the comparative example is evenly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The nano-alumina-based antibacterial and mildewproof coating prepared by the comparative example is subjected to the mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Comparative example 3
The comparative example provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.5g of vanillin, 0.25g of SDS powder and 50g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the mixed solution of vanillin and nano alumina, and taking the mixed solution as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.6g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared by the comparative example is evenly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The nano-alumina-based antibacterial and mildewproof coating prepared by the comparative example is subjected to the mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Comparative example 4
The comparative example provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
0.5g of a commercially available alumina powder having a particle size of 3000mm, 0.5g of ascorbic acid, 0.25g of SDS powder and 50g of deionized water were weighed and placed in a beaker.
Setting the stirring speed at 300rpm and the stirring time at 37 ℃ for 3h, standing for 30min, and sucking out the solution to obtain a mixed solution of ascorbic acid and nano-alumina, wherein the mixed solution is used as modified nano-alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.6g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared by the comparative example is evenly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The nano-alumina-based antibacterial and mildewproof coating prepared by the comparative example is subjected to the mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Comparative example 5
The comparative example provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.5g of ascorbic acid, 0.25g of SDS powder and 50g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 3h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the ascorbic acid grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.02g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared by the comparative example is evenly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The nano-alumina-based antibacterial and mildewproof coating prepared by the comparative example is subjected to the mildewproof test according to GB-T1741-2007, and the results are shown in Table 1.
Comparative example 6
The comparative example provides an antibacterial and mildewproof coating based on nano aluminum oxide and a preparation method thereof. The method comprises the following specific steps:
(1) preparing modified nano-alumina:
50g of zirconia beads with the particle size of 0.1mm are taken and put into a ball milling pot with the volume of 100ml, 0.5g of alumina powder with the particle size of 3000mm sold in the market, 0.5g of ascorbic acid, 0.25g of SDS powder and 50g of deionized water are weighed and put into the ball milling pot.
Setting the speed of a ball mill (model: UBE-V2L, Hunan Germany and technology Limited) at 300rpm and the ball milling time at 4h at 37 ℃, closing the ball mill, standing for 30min, taking down the ball milling tank, sucking out the solution in the ball milling tank to obtain the ascorbic acid grafted nano alumina colloidal solution which is used as the modified nano alumina.
(2) Preparing the antibacterial and mildewproof coating based on the nano aluminum oxide:
at 37 ℃, 30g of commercial butylbenzene emulsion and 0.01g of modified nano-alumina are uniformly stirred at 600rpm to obtain the nano-alumina-based antibacterial and mildewproof coating.
The antibacterial and mildewproof paint based on nano aluminum oxide prepared by the comparative example is evenly sprayed on a glass plate with the thickness of 50 x 4mm, is cured for 48 hours at room temperature, and is subjected to an antibacterial test according to standard HG/T3950-2007 appendix A, and the result is shown in Table 1.
The nano-alumina-based antibacterial and mildewproof coating prepared by the comparative example is subjected to the mildewproof test according to GB-T1741-2007, and the results are shown in a chart 1.
The antibacterial and mildewproof nano alumina-based coatings prepared in examples 1 to 15 and comparative examples 2 to 6, and the antibacterial and mildewproof properties of the coating of comparative example 1 are shown in table 1.
TABLE 1
As can be seen from table 1, compared to comparative examples 1 to 6, the antibacterial and mildewproof paint based on nano alumina prepared in examples 1 to 15 has more excellent bacteriostatic effect and mildewproof effect on staphylococcus aureus and escherichia coli; the coating which is not added with the modified nano-alumina in the comparative example 1 has no bacteriostatic effect on staphylococcus aureus and escherichia coli, and the mildew-proof effect is very poor; comparative examples 2 and 3 do not adopt the modifier of the invention to carry out chemical modification on nano-alumina, and the prepared antibacterial and mildewproof coating has poor bacteriostatic effect on staphylococcus aureus and escherichia coli and poor mildewproof effect; comparative example 4 mechanical modification is not carried out on the nano-alumina by ball milling treatment, and the prepared antibacterial and mildewproof coating has poor bacteriostatic effect on staphylococcus aureus and escherichia coli and poor mildewproof effect. In comparative examples 5 and 6, the mass ratio of the emulsion to the nano-modified alumina was out of the range of the present invention, and the antibacterial property and the mildew resistance were deteriorated.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.
Claims (12)
1. An antibacterial and mildewproof coating is characterized by comprising an emulsion and modified nano aluminum oxide; the mass ratio of the emulsion to the modified nano-alumina is (50-1200): 1;
the preparation method of the modified nano-alumina comprises the following steps:
mixing the raw materials for preparing the modified nano-alumina, and carrying out ball milling treatment;
the raw materials comprise nano aluminum oxide, a modifier and a dispersant;
the modifier is selected from one or more of ascorbic acid, L-cysteine, L-arginine or L-alanine.
2. The antibacterial and antifungal coating of claim 1 wherein the emulsion is a styrene-butadiene emulsion, a vinyl acetate emulsion, a polyvinylidene chloride emulsion, or a polysulfide-vinylidene chloride emulsion.
3. The antibacterial and mildewproof coating as claimed in claim 1, wherein the mass ratio of the nano alumina to the modifier is (1-8): 1; and/or
The mass ratio of the nano aluminum oxide to the water is 1: (100-1000).
4. The antibacterial and mildewproof coating as claimed in claim 1, wherein ball milling media used for ball milling are zirconia beads with the particle size of 0.05mm to 0.5 mm; and/or
The mass ratio of the nano alumina to the ball milling medium is 1: (50-1000).
5. The antibacterial and mildewproof coating as claimed in claim 1, wherein the ball milling temperature is 20-40 ℃, the rotation speed of the ball milling is 200-500 rpm, and the time is 1-5 h.
6. The antibacterial and mildewproof coating as claimed in claim 1, wherein the nano alumina has a particle size of 2000nm to 8000 nm; and/or
The purity of the nano alumina is more than or equal to 99.99 percent; and/or
The purity of the modifier is BR grade.
7. The antibacterial and mildewproof coating according to any one of claims 1 to 6, wherein the raw materials for preparing the modified nano alumina further comprise a surfactant.
8. The antibacterial and mildewproof coating according to claim 7, wherein the surfactant is one or more selected from the group consisting of sodium dodecylbenzenesulfonate, sodium laurate, a silane coupling agent and tween 80; and/or
The mass ratio of the nano aluminum oxide to the surfactant is (1-10): 1.
9. the method for preparing the antibacterial and mildewproof coating according to any one of claims 1 to 8, comprising the steps of:
mixing the emulsion and the modified nano-alumina.
10. The method for preparing the antibacterial and mildewproof coating according to claim 9, wherein the emulsion and the modified nano aluminum oxide are mixed by mechanical stirring at a rotating speed of 500-1500 rpm.
11. An architectural coating characterized by comprising the antibacterial and mildewproof coating according to any one of claims 1 to 8.
12. A furniture coating characterized by comprising the antibacterial and mildewproof coating according to any one of claims 1 to 8.
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