CN112409871A - Antibacterial polymer-based waterproof coating and preparation method thereof - Google Patents
Antibacterial polymer-based waterproof coating and preparation method thereof Download PDFInfo
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- 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
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Abstract
The invention discloses an antibacterial polymer-based waterproof coating and a preparation method thereof, wherein an antibacterial agent material with good biological activity and antibacterial effect is obtained by loading nano silver and nano zinc oxide on a chitosan-calcium hydroxy phosphate composite material synthesized in situ, and then the antibacterial agent material is added into a formula of the polymer-based waterproof coating to obtain the antibacterial polymer-based waterproof coating, the chitosan-calcium hydroxy phosphate loaded nano silver and nano zinc oxide antibacterial agent synthesized in situ have uniform granularity and good dispersibility, can firmly load nano particles and can not fall off from a load body to be agglomerated again, the chitosan-calcium hydroxy phosphate loaded nano silver and nano zinc oxide antibacterial agent synthesized in situ have good compatibility with a polymer, and when the coating is prepared, the antibacterial additive can not be separated from a polymer matrix substance to cause the reduction of the coating performance and the antibacterial effect, meanwhile, the antibacterial agent modified by chitosan has optimized film-forming property when being added into a coating for use.
Description
Technical Field
The invention relates to the field of waterproof coatings, and particularly relates to an antibacterial polymer-based waterproof coating and a preparation method thereof.
Background
The polymer cement-based waterproof paint in the waterproof paint consists of emulsion synthesized by a plurality of water-based polymers and high-quality cement mixed with various additives, and the flexibility of the polymers and the rigidity of the cement are integrated, so that the waterproof paint has excellent impermeability, stability, durability and the like, and is convenient to construct, low in comprehensive cost, non-toxic and environment-friendly. However, many waterproof coatings are applied in humid and dark environments, and under such environments, various bacteria and mold are easily bred in organic components in the coatings, so that the waterproof coatings deteriorate and the waterproof performance is reduced. If the coating is left untreated for a long time, the water-proof property of the coating is lost.
At present, some antibacterial mildew-proof agents such as titanium dioxide with photocatalytic performance are usually added aiming at the antibacterial mildew-proof of the polymer waterproof coating, but the antibacterial mildew-proof agent can only play a role in sterilization under the irradiation of light, and cannot play a good role in the waterproof coating in a dark environment; the materials have good compatibility with organic polymers, high sterilization efficiency, but are not aging-resistant, the life cycle of common waterproof coatings is more than 5 years, and the organic bactericide is volatile, easy to decompose and poor in durability; inorganic bactericides such as nano silver, zinc oxide and the like have long action time and good bactericidal effect, but have poor compatibility with organic polymers, and easily enter an inorganic phase in the mixing process of the coating, so that the antibacterial capability of the organic polymers which are easy to grow bacteria is reduced.
Chinese patent publication No. CN105925103A discloses a method for producing an antibacterial paint, an antibacterial paint and a breathable antibacterial film containing the antibacterial paint, comprising the following steps: s1: weighing the materials in the raw material formula according to the parts by weight; s2: methyl cyclomethacrylate, butyl acrylate and nano TiO2Adding hydroxypropyl methacrylate sulfonic acid, acrylic resin, polyoxyethylene ether, an emulsifier, deionized water, a pH regulator and a film-forming auxiliary agent into a mixer for pre-stirring, wherein the stirring speed is 3000-6000 rpm/min, and the stirring time is 0.1-0.2 hours; s3: the mixed raw material obtained from S2 is sequentially subjected to melt extrusion of an extruder, tabletting and crushing of a tabletting machine, micro-crushing of a crusher and a rotary screen to finally become antibacterial coating powder, and nano TiO is adopted2As an antibacterial component, it is necessary to exert an antibacterial effect sufficiently under light conditions, and the antibacterial effect is not remarkable in a dark environment.
Chinese patent publication No. CN109825142A discloses an anti-mildew polymer cement waterproof coating, which is mainly added with didecyl dimethyl ammonium chloride, 2- (thiocyanomethylmercapto) benzothiazole and isothiazolinone organic mildew preventive to ensure that the waterproof coating has an anti-mildew function, but the organic mildew preventive is not aging-resistant, so that the anti-mildew time is short, and the life cycle of the waterproof coating cannot be met.
Chinese patent publication No. CN109810595A discloses a waterproof antibacterial coating, which is composed of the following components in parts by weight: 2-16 parts of simethicone, 4-10 parts of antibacterial nano particles, 24-40 parts of acrylate emulsion, 24-40 parts of polyurethane, 1-2 parts of nano titanium dioxide, 5-10 parts of permethrin, 6-16 parts of nano zinc, 3-8 parts of nano silver, 2-5 parts of sodium hexametaphosphate, 0.5-2 parts of nano silicon oxide, 3-8 parts of a dispersing agent and 1-2 parts of a flame retardant.
Chinese patent publication No. CN106280740A discloses an antibacterial interior wall coating, which comprises 23-26 parts of styrene-acrylic emulsion, 10-15 parts of 4% hydroxyethyl cellulose solution, 4-6 parts of nano-silver antibacterial agent, 10-22 parts of hydroxyapatite, 4-10 parts of nano-bentonite, 16-19 parts of talcum powder, 0.5-0.8 part of 2- (4-thiazole) benzimidazole, 0.8-1.2 parts of thickening agent, 0.5-3.5 parts of dispersing agent, 0.1-0.3 part of defoaming agent, 0.5-1 part of film forming auxiliary agent and 20-35 parts of deionized water, wherein the nano-silver antibacterial agent is loaded on the hydroxyapatite in the formula, but the granularity and the dispersion of the granules are not uniform enough and the loading effect is poor due to the fact that the hydroxyapatite and the nano-silver are loaded by directly adding the hydroxyapatite and utilizing the porous characteristic of the hydroxyapatite.
Disclosure of Invention
Aiming at the problems that the waterproof performance of the existing polymer waterproof coating is reduced due to easy bacteria growth and deterioration in a humid environment and the antibacterial coating in the prior art, the invention provides an antibacterial polymer-based waterproof coating and a preparation method thereof. The invention utilizes the chitosan-calcium hydroxy phosphate composite material which is synthesized in situ to load the nano silver and the nano zinc oxide to obtain the antibacterial agent material with good biological activity and antibacterial effect, and then the antibacterial agent material is added into the formula of the polymer-based waterproof coating to obtain the antibacterial polymer-based waterproof coating. Specifically, after sodium hydrogen phosphate is added into water to be dissolved, nano silver and nano zinc oxide are continuously added, stirring and dispersing are carried out, then chitosan acetic acid solution is slowly dripped, after uniform mixing, saturated calcium nitrate solution is dripped at a constant speed, after dripping is finished, ammonia water is used for adjusting the pH value to 10-11, after stirring is carried out for 1-2 hours, standing is carried out for 10-11 hours at room temperature, filtering is carried out, vacuum drying is carried out at 100 ℃, crushing is carried out, and a 100-mesh sieve is screened, so that the chitosan-calcium hydroxy phosphate composite material loaded nano silver and nano zinc oxide antibacterial agent is obtained. According to the invention, the chitosan-calcium hydroxy phosphate composite material is used for loading the nano silver and nano zinc oxide antibacterial agent, so that the biological activity of the antibacterial material is improved; the antibacterial additive prepared by the chitosan-calcium hydroxyphosphate loaded with nano silver and nano zinc oxide synthesized in situ has more uniform granularity and good dispersibility in the coating, and can firmly load nano particles without falling off from a load and reuniting; the antibacterial additive prepared by the chitosan modified calcium hydroxy phosphate loaded with the nano silver and the nano zinc oxide has higher compatibility with the polymer, and the reduction of the performance and the antibacterial effect caused by phase separation when the antibacterial additive is added into the coating is avoided; the composite antibacterial material modified by chitosan enables the nano silver and the nano zinc oxide to be compatible with the polymer, so that the antibacterial performance of the polymer is improved, and meanwhile, the nano silver and the nano zinc oxide are prepared into the mixed bactericide, so that the use of expensive silver can be reduced, the cost is reduced, and the actual production requirements are met.
A preparation method of an antibacterial polymer-based waterproof coating is characterized by comprising the following steps:
(1) adding sodium hydrogen phosphate into water to dissolve, continuously adding nano silver and nano zinc oxide, stirring and dispersing, then slowly dropwise adding a chitosan acetic acid solution, uniformly mixing, dropwise adding a saturated calcium nitrate solution at a constant speed, adjusting the pH to 10-11 by using ammonia water after dropwise adding is finished, continuously stirring for 1-2 hours, standing for 10-11 hours at room temperature, filtering, then performing vacuum drying at 100 ℃, crushing, and sieving with a 100-mesh sieve to obtain a chitosan-calcium hydroxy phosphate composite material loaded nano silver and nano zinc oxide antibacterial agent; loading nano silver and nano zinc oxide into chitosan modified calcium hydroxy phosphate by an in-situ synthesis mode, the calcium hydroxy phosphate is formed by taking the nano particle as a core, the generated calcium hydroxy phosphate is coated around the nano particle, because the calcium hydroxy phosphate almost grows and forms simultaneously by taking countless nano particles in the solution as the cores, the growth of the coated particles is more uniform, the sizes of the generated additive particles are more consistent, the additive particles modified by chitosan have good compatibility with the polymer, the modified additive particles can be uniformly dispersed in the coating, in addition, the nano silver and zinc oxide particles and the chitosan modified calcium hydroxy phosphate are combined to form a coating structure in an in-situ synthesis mode, so that stable load on the nano particles can be formed, and the nano particles cannot be reunited to further reduce the performance and the antibacterial effect of the coating because the nano particles fall off from a load body when the antibacterial additive is prepared into the coating and used. And chitosan is a substance with good film forming property, and the chitosan modified antibacterial agent has optimized film forming property when being added into the coating and used, so that a uniform coating of the coating can be formed.
(2) And (2) mixing and uniformly stirring the antibacterial agent obtained in the step (1), propyl benzene emulsion, vinyl acetate-acrylic emulsion, preservative, dispersing agent, defoaming agent, water, silicate cement, quartz sand, wollastonite, cellulose ether and water reducing agent to obtain the antibacterial polymer-based waterproof coating.
Preferably, the weight parts of the sodium hydrogen phosphate, the water, the nano silver, the nano zinc oxide, the chitosan acetic acid solution and the saturated calcium nitrate solution in the step (1) are 3-8, 10-20, 2-6, 5-10 and 5-10.
Preferably, the preservative in step (2) is s786 or k9 n.
Preferably, the dispersant in the step (2) is a sodium polyacrylate dispersant.
Preferably, the defoaming agent in the step (2) is a silicone defoaming agent Foamic-042 defoaming agent.
Preferably, the cellulose ether in the step (2) is hydroxyethyl methyl cellulose ether or hydroxypropyl methyl cellulose ether, and the viscosity is 20000 mPa.s-40000 mPa.s.
Preferably, the water reducing agent in the step (2) is a sulfonated melamine high-efficiency water reducing agent or a polycarboxylic acid water reducing agent.
Preferably, the antibacterial agent and the propyl benzene emulsion, the vinyl acetate-acrylic emulsion, the preservative, the dispersing agent, the defoaming agent, the water, the silicate cement, the quartz sand, the wollastonite, the cellulose ether and the water reducing agent in the step (2) are 1-5 parts, 30-40 parts, 0.2-0.5 part, 0.1-0.3 part, 4-8 parts, 30-50 parts, 15-25 parts, 5-10 parts, 0.05-0.1 part and 0.5-1 part by weight.
The antibacterial polymer-based waterproof coating prepared by the method.
According to the invention, nano silver and nano zinc oxide are loaded into chitosan modified calcium hydroxy phosphate in an in-situ synthesis manner, the calcium hydroxy phosphate is formed by taking nano particles as cores, the generated calcium hydroxy phosphate is coated around the nano particles, and the calcium hydroxy phosphate is formed by almost simultaneously growing by taking countless nano particles in a solution as cores, so that the coated particles grow uniformly, the sizes of the generated additive particles are more consistent, the compatibility of the chitosan modified additive particles and a polymer is better, and the modified additive particles can be uniformly dispersed in a coating. In addition, the nano silver and zinc oxide particles and the chitosan modified calcium hydroxy phosphate are combined to form a coating structure in an in-situ synthesis mode, so that stable load on the nano particles can be formed, and the nano particles cannot be reunited to further reduce the performance and the antibacterial effect of the coating because the nano particles fall off from a load body when the antibacterial additive is prepared into the coating and used. The chitosan is a substance with good film forming property, and the antibacterial agent modified by the chitosan has optimized film forming property when being added into the paint and used, and is beneficial to forming a uniform paint coating when being brushed.
The invention utilizes the chitosan-calcium hydroxy phosphate composite material which is synthesized in situ to load the nano silver and the nano zinc oxide to obtain the antibacterial agent material with good biological activity and antibacterial effect, and then the antibacterial agent material is added into the formula of the polymer-based waterproof coating to obtain the antibacterial polymer-based waterproof coating.
According to the invention, the chitosan-calcium hydroxy phosphate composite material is used for loading the nano silver and nano zinc oxide antibacterial agent, so that the biological activity of the antibacterial material is improved; the antibacterial additive prepared by the chitosan-calcium hydroxyphosphate loaded with nano silver and nano zinc oxide synthesized in situ has more uniform granularity and good dispersibility in the coating, and can firmly load nano particles without falling off from a load and reuniting; the antibacterial additive prepared by the chitosan modified calcium hydroxy phosphate loaded with the nano silver and the nano zinc oxide has higher compatibility with the polymer, and the reduction of performance and antibacterial effect caused by phase separation after the antibacterial additive is added into the coating is avoided; after the chitosan modified antibacterial agent is used in the coating, the coating is endowed with excellent film-forming property, so that the coating is easy to form a uniform coating; the composite antibacterial material modified by chitosan enables the nano silver and the nano zinc oxide to be compatible with the polymer, so that the antibacterial performance of the polymer is improved, and meanwhile, the nano silver and the nano zinc oxide are prepared into the mixed bactericide, so that the use of expensive silver can be reduced, the cost is reduced, and the actual production requirements are met.
Has the advantages that:
(1) the antibacterial additive prepared by the chitosan-calcium hydroxyphosphate loaded with nano silver and nano zinc oxide synthesized in situ has more uniform granularity and good dispersibility in the coating, can firmly load nano particles, can not fall off from a load body and reunite, and can effectively improve the performance and antibacterial effect of the coating.
(2) The antibacterial additive prepared by the chitosan-modified calcium hydroxy phosphate loaded nano silver and nano zinc oxide has higher compatibility with a polymer, and avoids the reduction of performance and antibacterial effect caused by phase separation after the antibacterial additive is added into a coating.
(3) The chitosan is a substance with good film forming property, and the antibacterial agent modified by the chitosan has optimized film forming property when being added into the paint and used, and is beneficial to forming a uniform paint coating when being brushed.
(4) The mixed bactericide prepared from the nano silver and the nano zinc oxide can reduce the use of expensive silver, is favorable for reducing the cost and meets the actual production requirement.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
Adding 3 parts by weight of sodium hydrogen phosphate into 10 parts by weight of water for dissolving, continuously adding 2 parts by weight of nano silver and 2 parts by weight of nano zinc oxide, stirring and dispersing, slowly dropwise adding 5 parts by weight of chitosan acetic acid solution with the mass concentration of 10%, uniformly mixing, dropwise adding 5 parts by weight of saturated calcium nitrate solution at a constant speed, adjusting the pH to 11 by using ammonia water after dropwise adding, continuously stirring for 1 hour, standing for 10 hours at room temperature, filtering, then performing vacuum drying at 100 ℃, crushing and sieving by using a 100-mesh sieve to obtain the chitosan-calcium hydroxy phosphate composite material loaded nano silver and nano zinc oxide antibacterial agent. 1 part by weight of an antibacterial agent, 30 parts by weight of propyl benzene emulsion with the solid content of 57%, 30 parts by weight of vinyl acetate-acrylic emulsion with the solid content of 55%, 0.2 part by weight of a preservative s786, 0.2 part by weight of a sodium polyacrylate salt dispersant, 0.1 part by weight of a Foamic-042 defoaming agent, 4 parts by weight of water, 30 parts by weight of portland cement, 15 parts by weight of quartz sand, 5 parts by weight of wollastonite, 0.05 part by weight of hydroxyethyl methyl cellulose ether and 0.5 part by weight of a sulfonated melamine high-efficiency water reducing agent are mixed and stirred uniformly to obtain the antibacterial polymer-based waterproof coating.
Example 2
Adding 4 parts by weight of sodium hydrogen phosphate into 12 parts by weight of water for dissolving, continuously adding 3 parts by weight of nano silver and 3 parts by weight of nano zinc oxide, stirring and dispersing, slowly dropwise adding 6 parts by weight of chitosan acetic acid solution with the mass concentration of 10%, uniformly mixing, dropwise adding 6 parts by weight of saturated calcium nitrate solution at a constant speed, adjusting the pH to 10 by using ammonia water after dropwise adding, continuously stirring for 2 hours, standing for 11 hours at room temperature, filtering, then performing vacuum drying at 100 ℃, crushing and sieving by using a 100-mesh sieve to obtain the chitosan-calcium hydroxy phosphate composite material loaded nano silver and nano zinc oxide antibacterial agent. 2 parts by weight of an antibacterial agent, 33 parts by weight of propyl benzene emulsion with the solid content of 57%, 32 parts by weight of vinyl acetate-acrylic emulsion with the solid content of 55%, 0.3 part by weight of a preservative s786, 0.3 part by weight of a sodium polyacrylate salt dispersant, 0.15 part by weight of a Foamic-042 defoaming agent, 5 parts by weight of water, 35 parts by weight of portland cement, 17 parts by weight of quartz sand, 7 parts by weight of wollastonite, 0.06 part by weight of hydroxyethyl methyl cellulose ether and 0.7 part by weight of a sulfonated melamine high-efficiency water reducing agent are mixed and stirred uniformly to obtain the antibacterial polymer-based waterproof coating.
Example 3
Adding 6 parts by weight of sodium hydrogen phosphate into 15 parts by weight of water to dissolve, continuously adding 4 parts by weight of nano silver and 4 parts by weight of nano zinc oxide, stirring and dispersing, slowly dropwise adding 8 parts by weight of chitosan acetic acid solution with the mass concentration of 10%, uniformly mixing, dropwise adding 8 parts by weight of saturated calcium nitrate solution at a constant speed, adjusting the pH to 10 by using ammonia water after dropwise adding, continuously stirring for 1 hour, standing for 10 hours at room temperature, filtering, then performing vacuum drying at 100 ℃, crushing and sieving by using a 100-mesh sieve to obtain the chitosan-calcium hydroxy phosphate composite material loaded nano silver and nano zinc oxide antibacterial agent. 3 parts by weight of an antibacterial agent, 36 parts by weight of propyl benzene emulsion with the solid content of 57%, 35 parts by weight of vinyl acetate-acrylic emulsion with the solid content of 55%, 0.3 part by weight of a preservative s786, 0.4 part by weight of a sodium polyacrylate salt dispersant, 0.2 part by weight of a Foamic-042 defoaming agent, 6 parts by weight of water, 40 parts by weight of portland cement, 20 parts by weight of quartz sand, 8 parts by weight of wollastonite, 0.07 part by weight of hydroxypropyl methyl cellulose ether) and 0.8 part by weight of a sulfonated melamine high-efficiency water reducing agent are mixed and stirred uniformly to obtain the antibacterial polymer-based waterproof coating.
Example 4
Adding 7 parts by weight of sodium hydrogen phosphate into 17 parts by weight of water for dissolving, continuously adding 5 parts by weight of nano silver and 5 parts by weight of nano zinc oxide, stirring and dispersing, slowly dropwise adding 9 parts by weight of chitosan acetic acid solution with the mass concentration of 10%, uniformly mixing, dropwise adding 9 parts by weight of saturated calcium nitrate solution at a constant speed, adjusting the pH to 11 by using ammonia water after dropwise adding, continuously stirring for 2 hours, standing for 11 hours at room temperature, filtering, then performing vacuum drying at 100 ℃, crushing and sieving by using a 100-mesh sieve to obtain the chitosan-calcium hydroxy phosphate composite material loaded nano silver and nano zinc oxide antibacterial agent. 4 parts by weight of an antibacterial agent, 38 parts by weight of propyl benzene emulsion with the solid content of 57%, 38 parts by weight of vinyl acetate-acrylic emulsion with the solid content of 55%, 0.4 part by weight of a preservative k9n, 0.4 part by weight of a sodium polyacrylate salt dispersing agent, 0.25 part by weight of a Foamic-042 defoaming agent, 7 parts by weight of water, 45 parts by weight of portland cement, 23 parts by weight of quartz sand, 9 parts by weight of wollastonite, 0.08 part by weight of hydroxypropyl methyl cellulose ether and 0.9 part by weight of a polycarboxylic acid water reducing agent are mixed and stirred uniformly to obtain the antibacterial polymer-based waterproof coating.
Example 5
Adding 8 parts by weight of sodium hydrogen phosphate into 20 parts by weight of water for dissolving, continuously adding 6 parts by weight of nano silver and 6 parts by weight of nano zinc oxide, stirring and dispersing, slowly dropwise adding 10 parts by weight of chitosan acetic acid solution with the mass concentration of 10%, uniformly mixing, dropwise adding 10 parts by weight of saturated calcium nitrate solution at a constant speed, adjusting the pH to 11 with ammonia water after the dropwise adding is finished, continuously stirring for 1 hour, standing for 10 hours at room temperature, filtering, then performing vacuum drying at 100 ℃, crushing and sieving with a 100-mesh sieve to obtain the chitosan-calcium hydroxy phosphate composite material loaded nano silver and nano zinc oxide antibacterial agent. 5 parts by weight of an antibacterial agent, 40 parts by weight of propyl benzene emulsion with the solid content of 57%, 40 parts by weight of vinyl acetate-acrylic emulsion with the solid content of 55%, 0.5 part by weight of a preservative k9n, 0.5 part by weight of a sodium polyacrylate salt dispersing agent, 0.3 part by weight of a Foamic-042 defoaming agent, 8 parts by weight of water, 50 parts by weight of portland cement, 25 parts by weight of quartz sand, 10 parts by weight of wollastonite, 0.1 part by weight of hydroxypropyl methyl cellulose ether and 1 part by weight of a polycarboxylic acid water reducing agent are mixed and stirred uniformly to obtain the antibacterial polymer-based waterproof coating.
Comparative example 1
1 part by weight of a nano silver and nano zinc oxide mixed antibacterial agent prepared according to a ratio of 1:1, 30 parts by weight of propyl benzene emulsion with a solid content of 57%, 30 parts by weight of vinyl acetate-acrylic emulsion with a solid content of 55%, 0.2 part by weight of preservative s786, 0.2 part by weight of sodium polyacrylate dispersant, 0.1 part by weight of Foamic-042 defoamer, 4 parts by weight of water, 30 parts by weight of silicate cement, 15 parts by weight of quartz sand, 5 parts by weight of wollastonite, 0.05 part by weight of hydroxyethyl methyl cellulose ether and 0.5 part by weight of sulfonated melamine high-efficiency water reducer are mixed and stirred uniformly to obtain the antibacterial polymer-based waterproof coating.
And (4) relevant testing: refer to the national standard GB/T21866-2008 antibacterial coating (paint film) antibacterial performance measurement method and antibacterial effect.
The test method comprises the following steps: the coatings prepared in the examples and the comparative examples are respectively coated on a cement board with the thickness of 50mm multiplied by 50mm, a coating film is prepared according to the requirements of GB/T1727, the coating is coated twice, the first surface is dried and then coated for the second time, and the total thickness of the coating film is 90 mu m in a wet film. After painting, the coating was dried for 7 days under the conditions specified in GB/T9278. Before the experiment, an ultraviolet sterilizing lamp and medical alcohol are adopted to sterilize the surface of the paint film. Staphylococcus aureus and Escherichia coli were used as test strains, which were inoculated on the paint film and cultured at 37 ℃ under a relative humidity of 90% for 24 hours. Taking out the cultured sample, adding 20ml of washing solution respectively, repeatedly washing, inoculating the washing solution into nutrient agar culture medium, culturing at 37 deg.C for 24 hr, and counting viable bacteria. The bacterial count was determined by a microbial limit detector. Each test protocol was used to prepare a blank sample, and the antibacterial ratio was calculated by counting the number of colonies after culturing the coated and uncoated blank samples of the examples (comparative examples), and the test results are shown in Table 1 below.
Table 1:
according to experimental results, the antibacterial rate of the coating in example 1 to escherichia coli and staphylococcus aureus is about 12% higher than that of the coating in comparative example 1, the bioactivity of the antibacterial material is improved by in-situ synthesis of the chitosan-calcium hydroxyphosphate loaded with the nano-silver and nano-zinc oxide antibacterial agent, and the antibacterial agent particles are uniform in particle size, good in dispersity, stable in loaded structure, good in compatibility with the polymer and optimal in film forming property, so that the antibacterial agent additive particles can be stably and uniformly distributed in the coating to play the antibacterial action of the additive particles to the maximum extent, and the antibacterial property of the polymer coating film is improved.
Claims (9)
1. A preparation method of an antibacterial polymer-based waterproof coating is characterized by comprising the following steps:
(1) adding sodium hydrogen phosphate into water to dissolve, continuously adding nano silver and nano zinc oxide, stirring and dispersing, then slowly dropwise adding a chitosan acetic acid solution, uniformly mixing, dropwise adding a saturated calcium nitrate solution at a constant speed, adjusting the pH to 10-11 by using ammonia water after dropwise adding is finished, continuously stirring for 1-2 hours, standing for 10-11 hours at room temperature, filtering, then performing vacuum drying at 100 ℃, crushing, and sieving with a 100-mesh sieve to obtain a chitosan-calcium hydroxy phosphate composite material loaded nano silver and nano zinc oxide antibacterial agent;
(2) and (2) mixing and uniformly stirring the antibacterial agent obtained in the step (1), propyl benzene emulsion, vinyl acetate-acrylic emulsion, preservative, dispersing agent, defoaming agent, water, silicate cement, quartz sand, wollastonite, cellulose ether and water reducing agent to obtain the antibacterial polymer-based waterproof coating.
2. The method for preparing the antibacterial polymer-based waterproof coating material according to claim 1, characterized in that: the weight parts of the sodium hydrogen phosphate, the water, the nano silver, the nano zinc oxide, the chitosan acetic acid solution and the saturated calcium nitrate solution in the step (1) are 3-8, 10-20, 2-6, 5-10 and 5-10.
3. The method for preparing the antibacterial polymer-based waterproof coating material according to claim 1, characterized in that: the preservative in the step (2) is a preservative s786 or k9 n.
4. The method for preparing the antibacterial polymer-based waterproof coating material according to claim 1, characterized in that: the dispersant in the step (2) is a sodium polyacrylate dispersant.
5. The method for preparing the antibacterial polymer-based waterproof coating material according to claim 1, characterized in that: the defoaming agent in the step (2) is an organic silicon defoaming agent Foamic-042 defoaming agent.
6. The method for preparing the antibacterial polymer-based waterproof coating material according to claim 1, characterized in that: the cellulose ether in the step (2) is hydroxyethyl methyl cellulose ether or hydroxypropyl methyl cellulose ether, and the viscosity is 20000 mPa.s-40000 mPa.s.
7. The method for preparing the antibacterial polymer-based waterproof coating material according to claim 1, characterized in that: the water reducing agent in the step (2) is a sulfonated melamine high-efficiency water reducing agent or a polycarboxylic acid water reducing agent.
8. The method for preparing the antibacterial polymer-based waterproof coating material according to claim 1, characterized in that: the antibacterial agent, the propyl benzene emulsion, the vinyl acetate-acrylic emulsion, the preservative, the dispersing agent, the defoaming agent, the water, the portland cement, the quartz sand, the wollastonite, the cellulose ether and the water reducing agent in the step (2) are 1-5 parts, 30-40 parts, 0.2-0.5 part, 0.1-0.3 part, 4-8 parts, 30-50 parts, 15-25 parts, 5-10 parts, 0.05-0.1 part and 0.5-1 part by weight.
9. An antibacterial polymer-based waterproof coating is characterized in that: prepared by the process of any one of claims 1 to 8.
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