CN111286273A - Novel long-acting broad-spectrum antibacterial multifunctional water-based building coating and preparation method thereof - Google Patents

Abstract

The invention discloses a novel long-acting broad-spectrum bacteriostatic and antibacterial multifunctional water-based building coating and a preparation method thereof, wherein the coating comprises the following raw materials: the paint is prepared by compounding materials such as water-based emulsion, pigment filler, water-based functional auxiliary agent, water-based nano composite antibacterial agent, deionized water and the like. The invention is environment-friendly, does not generate drug resistance, has no in vivo accumulation, and has long-acting broad-spectrum bacteriostasis and antibiosis and durability while forming effective protection and strong decoration by coating the surface of the base material. The invention further introduces nano metal ions with stable functional ions, prepares the water-based nano composite antibacterial agent by grafting and nano composite technology, and solves the defects of high toxicity, low activity, poor application performance in different environments and the like of the traditional antibacterial material product. The product disclosed by the invention can form an autonomous regulation and supply antibacterial and antibacterial base system in a severe environment, can inhibit microorganisms and bacteria from gathering and deriving mutually in a long-acting broad spectrum manner, and is an antibacterial, antibacterial and mildewproof material with long-acting property and ecotype.

Description

Novel long-acting broad-spectrum antibacterial multifunctional water-based building coating and preparation method thereof

Technical Field

The embodiment of the invention relates to the technical field of functional fine building materials, in particular to a novel long-acting broad-spectrum antibacterial multifunctional water-based building coating and a preparation method thereof.

Background

With the increasing importance of the country on environmental protection, the series of environmental protection laws and regulations are continuously implemented, the rapid development of modern capital construction continuously puts higher requirements on the properties and functions of building materials, and the requirements all play a role in promoting the transformation and upgrading of the building material industry. The building protective coating which is one of the important external protection means of building matrix facilities is developing towards the water-based, high-performance, multifunctional, pollution-free, long-life and the like nowadays with increasing importance on environmental safety and environmental protection indexes.

Along with the importance of human health and hygiene, people are more and more concerned about the living environment in the future, and the maintenance of the environment without pollution is a feasible measure for preventing bacteria and viruses from invading human beings. The water-based building coating has the characteristics of excellent film-forming property, environmental friendliness and the like, and is widely applied to capital construction, but in the preparation and storage processes of the water-based building coating, a large amount of water is needed, the water is the most basic nutrient element of microorganisms, after film formation, in natural environments under various conditions, building material substrates and concrete products are eroded by chemical substances and microorganisms in the environment, and a film layer formed by the coating has certain gaps, so that bacteria and microorganism erosion are easily formed, microorganism aggregation and derivation are caused to form erosion and mildew, the protection and decoration attractiveness of buildings are seriously affected, the environmental health is harmed, and the use of antibacterial and antibacterial agents is the most simple, feasible and effective method for realizing no environmental pollution.

Traditional building matrix antisepsis relies primarily on the generation of surfaces toxic to microorganisms, rendering them incapable of habitation. The common anti-adhesion toxins containing tin and copper, formaldehyde and compounds thereof have the core problems of single approach, poor static anti-microbial performance, short period effect, poor broad spectrum property and the like, are not enough to drive away or kill the fouling microorganisms which attempt to adhere to a substrate, cannot be degraded in the natural environment, seriously damages the environmental ecological environment and causes the accumulation in organisms in a food chain, so that the novel long-acting broad-spectrum antibacterial product is developed, and the state technical monopoly is broken.

The increasing shortage of water resources and the increasing emphasis on the problem of microorganisms in cooling water systems make the development of novel and efficient industrial bactericides an important task, and meanwhile, the problem of the drug resistance of industrial bactericides is becoming more and more serious along with the increasing wide application of the bactericides in the industrial field, especially in areas with certain history of continuous use of the same bactericides, and the lack of reasonable use experience and professional guidance. How to overcome or delay the generation and development of microbial drug resistance so as to prolong the effective service life of the bactericide and reduce the pollution to the environment and water sources is an important problem in the use of the bactericide in various industries.

Resource conservation, energy conservation and emission reduction, ecological environment protection and low-carbon circular economy are basic modes of economic development, and with increasing shortage of water resources and increasing importance on the problem of microorganisms in a water system, the development of novel and efficient industrial antibacterial and bacteriostatic agents becomes a very important task. With the stricter environmental protection requirements in recent years, the nation requires the development of an environment-friendly antibacterial material, the dosage form develops towards the aspects of water-based, environmental protection, ultramicro, dust-free and controlled release, and the environment-friendly residue-free dosage form also becomes one of the directions for the technical development of antibacterial materials.

The traditional bactericide dosage form at present also has a plurality of defects, such as high cost, serious pollution to environment and water source due to the harmful toxic volatile substances such as VOC, aromatic hydrocarbon, heavy metal and the like, and unsatisfactory physical properties of certain varieties of antibacterial material dosage forms.

Disclosure of Invention

The invention aims to solve the technical problem of providing a novel long-acting broad-spectrum antibacterial multifunctional water-based building coating which can form effective protection on the surface of a coated substrate, has strong decoration, can realize the superposition of biological activity, increases the antibacterial, antibacterial and antifouling performances, has good degradability, no biological accumulation, no residue, no environmental pollution and no water source, is safe to operate, has strong stability and has remarkable antibacterial and antibacterial performances.

The technical problem to be solved by the invention is to provide a preparation method of a novel long-acting broad-spectrum antibacterial multifunctional water-based building coating, which has the advantages of simple preparation process and easy implementation, so that the novel long-acting broad-spectrum antibacterial multifunctional water-based building coating which can form effective protection on the surface of a coated substrate, has strong decoration, can realize superposition of biological activity, increases the antibacterial, antibacterial and antifouling performances, has good degradability, no biological accumulation, no residue, no environmental pollution and water source, safe operation, strong stability and remarkable antibacterial and antibacterial performances can be efficiently and energy-saving prepared.

In order to solve the technical problems, the invention provides the following technical scheme: the invention relates to a novel long-acting broad-spectrum antibacterial multifunctional water-based building coating, which comprises the following technical measures in percentage by mass: the production raw materials comprise the following components in percentage by mass: 20-25% of aqueous dispersion emulsion, 5-15% of aqueous odor-free emulsion, 1-3% of pigment, 20-30% of lead-free filler, 0.2-0.5% of aqueous defoaming agent, 0.2-0.5% of aqueous wetting dispersant, 0.1-0.3% of surfactant, 0.2-0.5% of aqueous anti-fouling agent, 0.5-1% of thixotropic agent, 1-2% of aqueous nano composite antibacterial agent, 0.1-0.5% of pH neutralizer, 0.5-1% of antifreezing agent, 0-1% of film-forming additive and 30-40% of deionized water.

Further, the aqueous dispersion emulsion can be one of natural plant alcohol-based modified aqueous dispersion emulsion, natural resin-based aqueous dispersion emulsion or a combination thereof;

further, the water-based odor-free emulsion is one or the combination of pure acrylic emulsion, hybrid graft crosslinking acrylic emulsion and organic silicon graft acrylic emulsion;

further, the pigment is one of titanium dioxide, natural plant extracted pigment and purified natural mineral pigment;

further, the lead-free filler is one or a combination of natural stone powder, calcium carbonate, talcum powder, barium sulfate, lithopone and calcined kaolin;

the aqueous defoaming agent is at least one of a high-grade natural policosanol defoaming agent and a high-grade natural myristyl alcohol-based defoaming agent with the carbon number of c 12-c 28;

furthermore, the aqueous wetting dispersant is one of aqueous siloxane-based wetting dispersant and aqueous nonionic alkynyl polyalcohol wetting dispersant;

further, the surfactant is one of nonionic gemini siloxane, pentadecylcyclopentasiloxane and amino modified polysiloxane;

further, the water-based anti-fouling agent is one of organic silicon modified polyacrylate polymer, water-based nano hybrid silicone oil and octyl triethoxy modified silicone oil;

further, the water-based nano composite antibacterial agent is a water-based nano composite antibacterial agent consisting of silver particles, zinc oxide, titanium dioxide, isothiazolinone, plant extract, ion exchanger, penetrant, solubilization stabilizer, synergist and deionized water;

further, the thixotropic agent is one of tamarind seed polysaccharide gum, natural cellulose derivative and guar gum enzymatic hydrolysate;

further, the pH neutralizer is one of succinic acid, 2-hydroxysuccinic acid and tartaric acid;

further, the antifreezing agent is one of medical grade propylene glycol and glycerol;

further, the film-forming assistant is one of hexadecane diester and 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate;

further, the deionized water may be tap water from which impurities are removed.

On the other hand, the invention also provides a preparation method of the novel long-acting broad-spectrum antibacterial multifunctional water-based building coating, which comprises the following steps:

in a high-low temperature dispersion reaction and mixing integrated kettle with a condenser, a dropping device, a stirrer and a thermometer, adding deionized water accounting for 35-65% of the total mass of the deionized water into a dispersion cylinder according to the mass percentage of a formula, sequentially adding a lead-free filler and a water-based wetting dispersant, stirring for 30-50 min at the rotating speed of 1200 and 1500rmp, uniformly dispersing until the fineness is less than 50 mu m, sequentially adding a water dispersion emulsion and a water-based odor-free emulsion at the rotating speed of 500-800 rmp, and continuously dispersing for 20-30 min with a water-based defoaming agent accounting for 50% of the total mass; adding a surfactant, a water-based anti-fouling agent and a thixotropic agent at a rotating speed of 300-500 rmp, continuously dispersing for 20-30 min, keeping the rotating speed, adding a water-based nano composite antibacterial and antibacterial agent, an antifreezing agent, a film forming aid, the rest of water-based defoaming agent and the rest of deionized water, continuously dispersing for 20-40 min, adding a pH neutralizer to adjust the pH value to 9 +/-0.5, detecting when the viscosity (Rotothrinner) is 6-8, filtering by using a filter with a screen mesh number of 80-120 meshes and packaging to obtain the novel broad-spectrum antibacterial and antibacterial multifunctional water-based architectural coating;

further, the water-based nano composite antibacterial agent comprises the following raw materials in percentage by weight: 1-2% of silver particles, 3-5% of zinc oxide, 5-10% of titanium dioxide, 5-10% of plant extract, 2-5% of isothiazolinone, 25-30% of ion exchanger, 1-2% of penetrant, 1-2% of solubilizing stabilizer, 1-2% of synergistic agent and 40-50% of deionized water;

the silver particles are powdery simple substance nano silver particles with the particle size of 25-50 nm, the zinc oxide is tetrapod-shaped zinc oxide whiskers of a lead-zinc ore single crystal type gas phase oxidation method, the titanium dioxide is anatase type nano titanium dioxide with the particle size of 10-30 nm, the plant extract is one of alomenadin, aloe tincture and chitosan, the isothiazolinone is one of pure medicament type 4, 5-dichloro-N-octyl-4-isothiazolinone with the technical indexes of 100% of solid content, 300-332.921 ℃ of boiling point, 42.2-42.8 ℃ of melting point, 100% of pure medicament type 2-octyl-4-isothiazolinone with the boiling point of 115-120 ℃ of relative density of water at 20 ℃ of 1.01-1.05, the ion exchanger is cyanogen oxygen pyrolysis method synthesized lead-free nano silicon dioxide with the median particle size of 30-70 nm, the ion exchanger is a synergic ion-free silicon dioxide nano silicon dioxide, the ion synthetic lead-free nano silicon dioxide (D50) is synthesized by a median oxygen pyrolysis method, the ion-free nano silicon dioxide, the ion solubilizing agent is a synergistic ion type 2-octyl-4-isothiazolinone with the median particle size of 2-acetic acid, the boiling point of a synergistic ion, the ion solubilizing agent with the median particle size of 2-7-8 ℃ of a synergistic effect of an anion-7-8 ℃, the ion, the ionic type 2-7-8 ℃ of an anion-acetyl alcohol, the ionic type of an amphoteric carbon dioxide is used as a synergistic ion solubilizing agent, the ionic type of an anion-7-8-acetyl.

Further, the water-based nano composite antibacterial agent is prepared by the following process:

in a pressure-reducing and pressure-resistant reaction vessel capable of stirring, heating, cooling, dropwise adding, replacing with nitrogen, pressurizing by using nitrogen and using a vacuum pump, adding deionized water accounting for 10-15% of the total mass of the deionized water into a dispersion reaction mixing kettle according to the mass percentage of the formula, then adding isothiazolinone, and dissolving at the rotating speed of 600-800 rmp to prepare isothiazolinone solution for later use;

under the protection of nitrogen, sequentially adding deionized water accounting for 15-20% of the total mass into a dispersion reaction mixing kettle at the temperature of 0 +/-15 ℃, sequentially adding silver particles, zinc oxide and titanium dioxide, uniformly stirring at the rotating speed of 200-300 rmp by magnetic stirring to prepare composite nano powder slurry, vacuumizing, filling nitrogen, and sealing for later use;

under the protection of nitrogen, adding deionized water, an ion exchanger and a penetrating agent which account for 15-20% of the total mass ratio at the temperature of 25 +/-5 ℃, and stirring at the rotating speed of 800-1200 rpm for 10-15 min; cooling to 0 +/-10 ℃, adding the composite nano powder slurry, magnetically stirring at the rotation speed of 200-300 rpm under the reduced pressure of 0.6-1.3 kpa, keeping the temperature and stirring for 10-15 min, heating to 90-110 ℃, keeping the temperature constant, and carrying out heat treatment reaction for 1.5-2.5 hr while stirring;

under the protection of nitrogen, dropwise adding the synergistic agent from a burette, stirring with a magnetic stirrer while dropwise adding until the powder is completely suspended, stopping the machine when the M value of the volume percentage of the liquid mixture is measured to be 40-60, dehydrating the mixture for 2-2.5 hours while stirring at low speed under the reduced pressure of 0.6-1.3 kpa, and stopping stirring when the water content is measured to be 2-3;

under the protection of nitrogen, cooling to 25 +/-5 ℃, adding the rest deionized water, the plant extract and the isothiazolinone solution sequentially at the beginning, wherein the dropping speed is 3-5L/min, then heating to 25-40 ℃, beginning to drop the solubilizing stabilizer, stirring at the rotating speed of 300-500 rpm by magnetic force after dropping at the speed of 20-30 drops/min is finished, keeping the temperature constant, continuing to stir for reaction for 1.5-2 hr, and then cooling to the normal temperature to obtain the aqueous nano composite antibacterial agent.

After the technical scheme is adopted, the invention at least has the following beneficial effects:

the change of space bacterial colony is closely related to the quality of ecological environment, the bacteriostatic and antibacterial agent is an indispensable sterilization mode with the most extensive dosage in the fields of petroleum industry, chemical industry, food industry, paint industry, textile printing and dyeing and the like, the activity efficiency of the antibacterial agent, the inhibition and killing efficiency of microorganisms, and even the quality and performance of products in the applied field are directly determined. The product of the invention is very key to effectively promote autonomous bacteriostasis and antibiosis, has broad-spectrum and long-acting inhibiting and killing effects on mould, fungus, heterotrophic bacteria, algae plants, fouling organisms of a water system and the like on the premise of ensuring the reliability and safety of the use of the product, and is specifically embodied in the following aspects:

1. is environment-friendly. The bacteriostatic, antibacterial, preservative and bactericidal agent has no accumulation of plants, organisms, soil and water sources, can be naturally degraded into nontoxic substances in the environment, does not cause water source and environment pollution, can effectively form a safe and efficient bacteriostatic, antibacterial, preservative and bactericidal system, can be quickly hydrolyzed, photodegraded and biodegraded to decompose in the environment under the lowest bacteriostatic concentration (MIC), thoroughly solves the problem that the traditional bacteriostatic agent contains metal ionic compounds such as extremely toxic organic arsenic and organic tin, does not contain volatile and residues harmful to the natural environment, can be quickly hydrolyzed, photodegraded and biodegraded to decompose particularly, does not generate an accumulative effect, and overcomes the defects and the defects of common bacteriostatic and antibacterial coating products in the using process, and can not thoroughly remove harmful substances.

2. The technology is innovative. On the basis of the existing single photocatalytic antibacterial mechanism and contact type antibacterial mechanism, on the premise of ensuring the reliability and safety of product use, a compound technical combined antibacterial material medicament is developed, theoretical research on the antibacterial mechanism is strengthened on the basis of the existing single bactericide, the research on the action mechanism and synergistic effect of functional ions and medicaments is emphasized, the defects and defects of the traditional single medicament in the use process can be overcome, and meanwhile, the preparation method has the advantages of low production and preparation technical cost, good antibacterial effect, no toxic or side effect, no residue, no environmental pollution and no water source, and has important significance for promoting the technical transformation and upgrading of the antibacterial material industry and achieving the progress of capacity upgrading in the industrial field.

3. Antibacterial and long-acting broad spectrum. The technology of the invention adopts functional electrostatic ions of compound semiconductor materials with wide forbidden bands II-VI: the simple substance nano silver, the anti-oxidation zinc and the nano titanium dioxide have unique surface effect, small size effect, macroscopic quantum tunnel effect and the like, so that the crystal has incomparable special performance and new application in the aspects of magnetism, light, electricity, sensitivity and the like, and shows remarkable antibacterial property without illumination in a neutral environment, and has excellent broad-spectrum, high-efficiency and all-around microorganism capturing capability. The technology of the invention particularly utilizes nano-silica with large specific surface area, surface multi-mesoporous structure, super strong adsorption capacity and singular physical and chemical properties as a mesoporous ion exchanger, combines multiple environment-friendly antibacterial and mildewproof agents, adopts a grafting ion exchange embedding technology, fully utilizes complementary advantages among materials, can be compatible with various chemical industrial materials, surfactants and protein components, constructs an active antibacterial and bacteriostatic system with effective component activity superposition and enhanced sterilization mechanism, can realize that after contacting harmful microorganisms in different application fields, the growth of the active antibacterial and bacteriostatic system can be inhibited irreversibly by breaking bonds of bacteria and algae proteins, thereby leading to death of microbial cells and rapidly achieving ideal anticorrosive and bactericidal effects.

4. Has wide application. The application fields of the antibacterial materials are expanded from coatings, textiles, wood, paper, petroleum products, adhesives and the like to plastics, glass, ceramic metal and aerospace parts and the like, almost all the fields of the antibacterial materials are not separated, and various antibacterial agents are widely applied to the fields of coatings, cooling circulating water, metal processing liquid, washing products, adhesives, paper pulp, textiles, plastics and the like and become one of the most effective means for protecting various industrial materials and products from being harmed by microorganisms. The product can achieve physical mutual solubility with chlorine, a corrosion inhibitor, a scale inhibition dispersant, most of anions, cations, non-ions and other components, does not generate drug resistance after long-term use in a water system, has a remarkable effect on stripping of microorganism slime, can simultaneously inhibit microorganisms such as mold, bacteria, fungi, mold and the like in cooperation with other components, can still effectively inhibit the growth of bacteria, fungi and algae in high and low temperature and cooling water under the condition of very low concentration of effective components, can realize the superposition of biological activity when the medicament is diluted to be below the use concentration, increases the antibacterial performance of the medicament, widens the application field of the medicament, and is incomparable with other medicaments.

5. Broad-spectrum antibacterial and bactericidal performance and long-acting stability in wide application environments. The product of the invention introduces nano metal ions with stable functional ions, and effectively reduces the crystallinity of the polymer through the preparation technology of grafting and nano composite technology treatment, so that the melting temperature point of the polymer is reduced, and the defects of high and low temperature, poor application performance in different environments and the like of the traditional antibacterial material product are overcome. The electrons in the valence band of the functional ions can be excited to a conduction band to form freely moving electrons with negative charge and holes with positive charge, the holes react with oxygen, hydroxyl, water and the like adsorbed on the surface of the material to generate hydroxyl radicals and active oxygen ions with reduction effects such as hydroxyl, oxyanion, hydrogen peroxide and the like, and the constructed antibacterial and antibacterial system can be completely competent in a plurality of severe environments, can obviously improve the processing performance of the antibacterial and antibacterial system, and still shows excellent physical properties particularly in various severe environments such as high and low temperature, acid and alkali, humidity, darkness and the like.

The functional ion metal nano polymer has unique physical properties such as liquid temperature range, low volatility, high static viscosity, very low vapor pressure, low temperature flow temperature, high pressure stability and the like, is widely concerned by polymer scientists and industrial departments, becomes one of polymer types which are most researched and widely applied in molecular structure regular polymers, and also becomes an object of intercross research of a plurality of subjects such as chemistry, chemical engineering, petroleum, medicine, materials, physics, electronics, life science and the like, and the active polymerization causes high attention and great interest of chemical workers and polymer industry, and the research of the advantages in the direction of environmental protection and chemical industry, the method has a promoting effect on accelerating transformation and upgrading of the chemical industry, is a necessary product which is suitable for the increasing environmental awareness of people and the development of new technologies, and becomes an important development trend in the development direction in the future.

Detailed Description

The present invention will be described in further detail with reference to specific examples. It should be understood that the following illustrative embodiments and description are only intended to explain the present invention, and are not intended to limit the present invention, and features of the embodiments and examples in the present application may be combined with each other without conflict.

The invention provides a novel long-acting broad-spectrum antibacterial multifunctional water-based building coating, which comprises the following components in percentage by mass:

20-25% of aqueous dispersion emulsion

5-15% of water-based odor-free emulsion

1 to 3 percent of pigment

20-30% of lead-free filler

0.2 to 0.5 percent of water-based defoaming agent

0.2 to 0.5 percent of water-based wetting dispersant

0.1 to 0.3 percent of surfactant

0.2 to 0.5 percent of water-based anti-fouling agent

0.5 to 1 percent of thixotropic agent

1-2% of water-based nano composite antibacterial agent

0.1-0.5% of pH neutralizer

0.5 to 1 percent of antifreezing agent

0 to 1 percent of film forming additive

30-40% of deionized water

In an alternative embodiment of the invention, the aqueous dispersion emulsion can be one of natural plant alcohol-based modified aqueous dispersion emulsion, natural resin-based aqueous dispersion emulsion or a combination thereof;

in an optional embodiment of the invention, the aqueous odor-free emulsion is one or a combination of pure acrylic emulsion, hybrid graft-crosslinking acrylic emulsion and organic silicon graft-acrylic emulsion;

in an optional embodiment of the invention, the pigment is one of titanium dioxide, natural plant extracted pigment and purified natural mineral pigment;

in an alternative embodiment of the present invention, the lead-free filler is one or a combination of natural stone powder, calcium carbonate, talc powder, barium sulfate, lithopone and calcined kaolin;

in an optional embodiment of the invention, the aqueous antifoaming agent is at least one of a higher natural sugar cane alcohol-based antifoaming agent and a higher natural myristyl alcohol-based antifoaming agent with carbon number of c 12-c 28;

in an optional embodiment of the present invention, the aqueous wetting dispersant is one of an aqueous siloxane-based wetting dispersant and an aqueous nonionic alkynyl polyol wetting dispersant;

in an alternative embodiment of the present invention, the surfactant is one of nonionic gemini siloxane, pentadecylcyclopentasiloxane and amino modified polysiloxane;

in an optional embodiment of the invention, the aqueous anti-fouling agent is one of an organic silicon modified polyacrylate polymer, aqueous nano hybrid silicone oil and octyl triethoxy modified silicone oil;

in an optional embodiment of the invention, the aqueous nanocomposite antibacterial agent is an aqueous nanocomposite antibacterial agent composed of silver particles, zinc oxide, titanium dioxide, isothiazolinone, plant extract, ion exchanger, penetrant, solubilization stabilizer, synergist and deionized water;

in an alternative embodiment of the present invention, the thixotropic agent is one of tamarind polysaccharide gum, natural cellulose derivative, guar gum enzymatic hydrolysate;

in an alternative embodiment of the present invention, the pH neutralizer is one of succinic acid, 2-malic acid, tartaric acid;

in an alternative embodiment of the invention, the antifreeze is one of medical grade propylene glycol and glycerol;

in an alternative embodiment of the present invention, the coalescing agent is one of hexadecanediester, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate;

in an alternative embodiment of the present invention, the deionized water may be tap water from which impurities are removed.

The invention also provides several specific formulations as follows, wherein the percentages in the table are as follows:

although the components of the formula are slightly different, the technical effects of the obtained novel long-acting broad-spectrum antibacterial multifunctional water-based building coating are generally consistent.

On the other hand, the embodiment of the invention also provides a preparation method of the novel long-acting broad-spectrum antibacterial multifunctional water-based building coating, which comprises the following steps:

in a high-low temperature dispersion reaction and mixing integrated kettle with a condenser, a dropping device, a stirrer and a thermometer, adding deionized water accounting for 35-65% of the total mass of the deionized water into a dispersion cylinder according to the mass percentage of a formula, sequentially adding a lead-free filler and a water-based wetting dispersant, stirring for 30-50 min at the rotating speed of 1200 and 1500rmp, uniformly dispersing until the fineness is less than 50 mu m, sequentially adding a water dispersion emulsion and a water-based odor-free emulsion at the rotating speed of 500-800 rmp, and continuously dispersing for 20-30 min with a water-based defoaming agent accounting for 50% of the total mass; adding a surfactant, a water-based anti-fouling agent and a thixotropic agent at a rotating speed of 300-500 rmp, continuously dispersing for 20-30 min, keeping the rotating speed, adding a water-based nano composite antibacterial and antibacterial agent, an antifreezing agent, a film forming aid, the rest of water-based defoaming agent and the rest of deionized water, continuously dispersing for 20-40 min, adding a pH neutralizer to adjust the pH value to 9 +/-0.5, detecting when the viscosity (Rotothrinner) is 6-8, filtering by using a filter with a screen mesh number of 80-120 meshes and packaging to obtain the novel broad-spectrum antibacterial and antibacterial multifunctional water-based architectural coating.

The aqueous nano composite antibacterial agent adopted in the method comprises the steps of preparing in advance. The water-based nano composite antibacterial agent adopted in the method comprises the following raw materials in percentage by weight:

in the specific implementation, the silver particles are powdery simple substance nano silver particles with the particle size of 25-50 nm, the zinc oxide is tetrapod-shaped zinc oxide whiskers of a plumbite single crystal type and a gas phase oxidation method, the titanium dioxide is anatase type nano titanium dioxide with the particle size of 10-30 nm, the plant extract is one of alomorphan, aloe tincture and chitosan, the isothiazolinone is one of pure medicament type 4, 5-dichloro-N-octyl-4-isothiazolinone with the solid content of 100%, the boiling point of 300-332.921 ℃, the melting point of 42.2-42.8 ℃, the solid content of 100%, the boiling point of 115-120 ℃, the pure medicament type 2-octyl-4-isothiazolinone with the relative density of 1.01-1.05 to 20 ℃ of water, the ion exchanger is amorphous synthesized non-lead nano silver salt synthesized by a cyanothermolysis method with the median particle size of 30-70 nm, the silicon dioxide is non lead ion synthesized by a synergetic pyrolysis method, the amphoteric ion exchanger is a non lead ion silicon dioxide, the amphoteric ion exchanger is a synergistic agent with the ionic polysaccharide sulfate, the ionic phosphate ion, the amphoteric ion, the ionic silicon dioxide, the amphoteric ion exchanger is a synergistic agent with the boiling point of 2-alkyl alcohol, the ionic alcohol, the.

In specific implementation, the aqueous nano composite antibacterial agent can be prepared in advance according to the following preparation process:

in a pressure-reducing and pressure-resistant reaction vessel capable of stirring, heating, cooling, dropwise adding, replacing with nitrogen, pressurizing by using nitrogen and using a vacuum pump, adding deionized water accounting for 10-15% of the total mass of the deionized water into a dispersion reaction mixing kettle according to the mass percentage of the formula, then adding isothiazolinone, and dissolving at the rotating speed of 600-800 rmp to prepare isothiazolinone solution for later use;

under the protection of nitrogen, sequentially adding deionized water accounting for 15-20% of the total mass into a dispersion reaction mixing kettle at the temperature of 0 +/-15 ℃, sequentially adding silver particles, zinc oxide and titanium dioxide, uniformly stirring at the rotating speed of 200-300 rmp by magnetic stirring to prepare composite nano powder slurry, vacuumizing, filling nitrogen, and sealing for later use;

under the protection of nitrogen, adding deionized water, an ion exchanger and a penetrating agent which account for 15-20% of the total mass ratio at the temperature of 25 +/-5 ℃, and stirring at the rotating speed of 800-1200 rpm for 10-15 min; cooling to 0 +/-10 ℃, adding the composite nano powder slurry, magnetically stirring at the rotation speed of 200-300 rpm under the reduced pressure of 0.6-1.3 kpa, keeping the temperature and stirring for 10-15 min, heating to 90-110 ℃, keeping the temperature constant, and carrying out heat treatment reaction for 1.5-2.5 hr while stirring;

under the protection of nitrogen, dropwise adding the synergistic agent from a burette, stirring with a magnetic stirrer while dropwise adding until the powder is completely suspended, stopping the machine when the M value of the volume percentage of the liquid mixture is measured to be 40-60, dehydrating the mixture for 2-2.5 hours while stirring at low speed under the reduced pressure of 0.6-1.3 kpa, and stopping stirring when the water content is measured to be 2-3;

under the protection of nitrogen, cooling to 25 +/-5 ℃, adding the rest deionized water, the plant extract and the isothiazolinone solution sequentially at the beginning, wherein the dropping speed is 3-5L/min, then heating to 25-40 ℃, beginning to drop the solubilizing stabilizer, stirring at the rotating speed of 300-500 rpm by magnetic force after dropping at the speed of 20-30 drops/min is finished, keeping the temperature constant, continuing to stir for reaction for 1.5-2 hr, and then cooling to the normal temperature to obtain the aqueous nano composite antibacterial agent.

The novel long-acting broad-spectrum antibacterial multifunctional water-based building coating has the following beneficial effects:

1. green and environment-friendly, and excellent performance. The product of the invention belongs to water-based environment-friendly paint, adopts natural plant alcohol-based modified water-based dispersion emulsion and natural resin-based water dispersion emulsion as main base materials of the product, has almost zero contents of VOCs, formaldehyde, benzene, free monomers and organic pollutants, is environment-friendly in the whole process during production, manufacture and use of the product, and has no pollution and no harmful substances. The coating film has excellent performance, the waste paint film can be biodegraded, the degradation product has no harm to the environment, and the coating film can be widely applied to the decoration and protection of building engineering. Meets the limit of related documents such as GB/T35602-2017 green product evaluation coating, HJ/2537-

2. Antibacterial and long-acting broad spectrum. In the product standard state, the material meets GB/T30706-, HG/T3950-2007 antibacterial paint, SN/T2399-2010 antibacterial metal material evaluation method, SN/T3122-2012 inorganic antibacterial material antibacterial performance test method, ASTM G21-96(2002) Standard for testing the mildew-proof (fungus-resistant) performance of synthetic polymeric Material, SN/T2399-2010 antibacterial metal material evaluation method, JC/T1074-2008 indoor air purification function coating Material purification Performance, JC/T885-2016 (construction mildew-proof sealant), JIS R1702-2012 (ファインセラミックス -photocatalyst antibacterial processing product) antibacterial property test method-antibacterial fruit), JIS R1706-2013 (ファインセラミックス -photocatalyst material resistance ウイルス -test method- バクテリ), At home and abroad bacteriostatic and antibacterial standards such as JIS R1756-2013 "ファインセラミックス -architecture photo catalyst material of writable and writable structure ウイルス resistance test method", JIS Z2911-.

3. Is environment-friendly, does not generate drug resistance and has no in vivo accumulation. In the fields of coating industry, chemical industry, ship industry, food industry, petroleum industry, civil engineering and building industry, textile industry, paper industry, pharmaceutical industry or drainage treatment process and the like, the functional metal ion material is grafted and compounded by the composite antibacterial material, is used as a special high-performance material, is physically mutually soluble with chlorine, a corrosion inhibitor, a scale inhibition dispersant, most of anionic, cationic and nonionic surfactants and the like, is used for long-term bacteriostasis and antibiosis in a water system, and has a series of outstanding bacteriostasis and antibiosis long-acting broad-spectrum performances. The product of the invention is mainly used in key parts, resists severe environment, plays a special role, is an indispensable functional material for modern science and technology in many water system fields, particularly the used waste can be rapidly decomposed by hydrolysis, photodegradation and biodegradation in natural environment without residue and bioaccumulation, and can be naturally degraded into nontoxic substances in environment without causing water source and environmental pollution.

4. Has outstanding protective performance to the matrix. In the field of architectural coating industry protection in capital construction, special physicochemical conditions of the substrate need to be taken into account. In the natural environment under various conditions, building material matrixes and concrete products are eroded by chemical substances and microorganisms in the environment for a long time. The architectural protective coating is attached to the surface of the base material for a relatively long time, and the aesthetic decoration, the protective property and the like of the surface of the protective layer are closely related to the service life of the building. The product has the special effects of long-acting broad-spectrum autonomous antibacterial and protection except the due protection and decoration effects on a building matrix, has the performance of long-acting broad-spectrum prevention of mutual aggregation and derivation of microorganisms and bacteria, obviously improves the corrosion resistance, can form performance regulation to provide long-acting anti-corrosion effect, particularly has good inhibition effect on mould, fungus, heterotrophic bacteria and the like under the condition of humidity and darkness, protects the building matrix from being mildewed for a long time, achieves ideal long-acting broad-spectrum antibacterial and mildewproof effects, has high safety and lasting effect, and can greatly prolong the service life of the matrix. The nano metal functional ions have strong antibacterial and bacteriostatic properties, are combined on the surfaces of bacterial cells by the metal functional ions in the air, so that cell walls are damaged, the growth of the bacterial cells is prevented, thiol groups adsorbed to the bacteria lose proliferation and reproduction conditions in cellular enzymes, and aggregation and derivation of mould on a coated substrate are prevented for a long time.

5. The applicability is extremely wide, and the antifouling and algae removal performance of the water-based system in various environments is outstanding. The water-based nano composite antibacterial agent of the invention focuses on the research on the action mechanism and the synergistic effect of the agent, and makes up for the defects and shortcomings of a single agent in the using process. The product of the invention has good inhibition and killing effects on algae, marine fouling organisms, mould, fungi, heterotrophic bacteria and the like in fresh water and seawater systems. Particularly, the slow-release bactericide has excellent permeability, can quickly permeate into sediment to be decomposed when being added into a water system and released into the environment, has the function of capturing microorganisms by the aid of effective components which permeate into a substrate in all directions, plays a role in killing by breaking bonds of bacteria and algae proteins, can quickly and irreversibly inhibit growth of the microorganisms after being contacted with the microorganisms, so that microbial cells die, and has special slow-release bactericide sterilization performance in an upper space, so that the special slow-release bactericide can effectively prevent putrefaction and deterioration of the water system and a circulating aquatic product during storage, inhibit reproduction of the microorganisms and bacteria, and effectively kill bacteria, mold and fungi, and the performance of the slow-release bactericide is far higher than that of other similar products. In the field of ship industry, marine biofouling has plagued human development and application to the sea for many years, and prevention and control of marine biofouling also becomes a global problem and a research hotspot. Underwater navigation bodies such as ships, warships, submarines and the like are immersed in seawater for a long time, are corroded by the seawater, and have surfaces easy to be attached with marine organisms and polluted by marine attachments. The product of the invention meets the requirements of regulations of the World Health Organization (WHO), the United states environmental protection agency (U.S. environmental protection agency), Green Seal and the like, such as index requirements of emission limits of HAPs and Volatile organic Compounds, International controlled hazardous housing System convention (AFS convention) of IMO, Performance Standard of Ship ballast tank protective coating (PSPC), Bactericide product guide (BPD) of European Union, REACH and the like.

6. The novel long-acting broad-spectrum antibacterial multifunctional water-based building coating disclosed by the invention takes water as a matrix, is rich in water resources, is particularly simple in preparation method and process, and is convenient to package, store and transport, so that the industrialization cost is reduced, and the industrial production is facilitated.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various equivalent changes, modifications, substitutions and alterations can be made herein without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims (10)

1. A novel long-acting broad-spectrum antibacterial multifunctional water-based building coating is characterized by comprising the following raw materials in parts by mass: 20-25% of aqueous dispersion emulsion, 5-15% of aqueous odor-free emulsion, 1-3% of pigment, 20-30% of lead-free filler, 0.2-0.5% of aqueous defoaming agent, 0.2-0.5% of aqueous wetting dispersant, 0.1-0.3% of surfactant, 0.2-0.5% of aqueous anti-fouling agent, 0.5-1% of thixotropic agent, 1-2% of aqueous nano composite antibacterial agent, 0.1-0.5% of pH neutralizer, 0.5-1% of antifreezing agent, 0-1% of film-forming additive and 30-40% of deionized water.

2. The novel long-acting broad-spectrum bacteriostatic, antibacterial and multifunctional aqueous architectural coating according to claim 1, wherein the aqueous dispersion emulsion can be one of natural plant alcohol-based modified aqueous dispersion emulsion, natural resin-based aqueous dispersion emulsion or a combination thereof; the water-based odor-free emulsion is one or the combination of pure acrylic emulsion, hybrid graft cross-linking acrylic emulsion and organic silicon graft acrylic emulsion.

3. The novel long-acting broad-spectrum bacteriostatic and antibacterial multifunctional water-based architectural coating as claimed in claim 1, wherein the pigment is one of titanium dioxide, natural plant extracted pigment, purified natural mineral pigment; the lead-free filler is one or the combination of natural stone powder, calcium carbonate, talcum powder, barium sulfate, lithopone and calcined kaolin.

4. The novel long-acting broad-spectrum bacteriostatic, antibacterial and multifunctional water-based architectural coating according to claim 1, wherein the water-based antifoaming agent is at least one of a high-grade natural policosanol-based antifoaming agent and a high-grade natural myristyl alcohol-based antifoaming agent with carbon number of c 12-c 28; the water-based wetting dispersant is one of water-based siloxane-based wetting dispersant and water-based nonionic alkynyl polyalcohol wetting dispersant; the surfactant is one of nonionic gemini siloxane, pentadecylcyclopentasiloxane and amino modified polysiloxane; the water-based anti-fouling agent is one of organic silicon modified polyacrylate polymer, water-based nano hybrid silicone oil and octyl triethoxy modified silicone oil.

5. The novel long-acting broad-spectrum bacteriostatic and antibacterial multifunctional aqueous architectural coating according to claim 1, wherein the aqueous nano-composite bacteriostatic and antibacterial agent is an aqueous nano-composite bacteriostatic and antibacterial agent consisting of silver particles, zinc oxide, titanium dioxide, isothiazolinone, plant extract, ion exchanger, penetrant, solubilization stabilizer, synergist and deionized water.

6. The novel long-acting broad-spectrum bacteriostatic-antibacterial multifunctional aqueous architectural coating according to claim 1, wherein the thixotropic agent is one of tamarind polysaccharide gum, natural cellulose derivative, guar gum enzymatic hydrolysate; the pH neutralizer is one of succinic acid, 2-malic acid and tartaric acid; the antifreezing agent is one of medical-grade propylene glycol and glycerol; the film-forming auxiliary agent is one of hexadecanediester and 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the deionized water may be tap water from which impurities are removed.

7. The preparation method of the novel long-acting broad-spectrum antibacterial multifunctional water-based architectural coating as claimed in any one of claims 1 to 6, characterized by comprising the following steps: in a high-low temperature dispersion reaction and mixing integrated kettle with a condenser, a dropping device, a stirrer and a thermometer, adding deionized water accounting for 35-65% of the total mass of the deionized water into a dispersion cylinder according to the mass percentage of a formula, sequentially adding a lead-free filler and a water-based wetting dispersant, stirring for 30-50 min at the rotating speed of 1200 and 1500rmp, uniformly dispersing until the fineness is less than 50 mu m, sequentially adding a water dispersion emulsion and a water-based odor-free emulsion at the rotating speed of 500-800 rmp, and continuously dispersing for 20-30 min with a water-based defoaming agent accounting for 50% of the total mass; adding a surfactant, a water-based anti-fouling agent and a thixotropic agent at a rotating speed of 300-500 rmp, continuously dispersing for 20-30 min, keeping the rotating speed, adding a water-based nano composite antibacterial and antibacterial agent, an antifreezing agent, a film forming aid, the rest of water-based defoaming agent and the rest of deionized water, continuously dispersing for 20-40 min, adding a pH neutralizer to adjust the pH value to 9 +/-0.5, detecting when the viscosity (Rotothrinner) is 6-8, filtering by using a filter with a screen mesh number of 80-120 meshes and packaging to obtain the novel broad-spectrum antibacterial and antibacterial multifunctional water-based architectural coating.

8. A preparation method of a novel long-acting broad-spectrum antibacterial multifunctional water-based architectural coating as claimed in any one of claims 1 to 7, wherein the water-based nano-composite antibacterial agent adopted in the method is prepared in advance and comprises the following raw materials in percentage by weight: 1-2% of silver particles, 3-5% of zinc oxide, 5-10% of titanium dioxide, 5-10% of plant extract, 2-5% of isothiazolinone, 25-30% of ion exchanger, 1-2% of penetrant, 1-2% of solubilizing stabilizer, 1-2% of synergistic agent and 40-50% of deionized water.

9. The aqueous nano composite antibacterial and antibacterial agent according to claim 8, wherein the silver particles are powdery elemental nano silver particles with the particle size of 25-50 nm, the zinc oxide is tetrapod-shaped zinc oxide whiskers of a lead-zinc ore single crystal type gas phase oxidation method, the titanium dioxide is anatase type nano titanium dioxide with the particle size of 10-30 nm, the plant extract is one of alomomanthin, aloe tincture and chitosan, the isothiazolinone is one of pure pharmaceutical 4, 5-dichloro-N-octyl-4-isothiazolin-3-one with the technical indexes of solid content of 100%, boiling point of 300-332.921 ℃, melting point of 42.2-42.8 ℃, the ion exchanger is one of pure pharmaceutical 2-octyl-4-isothiazolin-3-one with solid content of 100%, boiling point of 115-120 ℃, relative density of 1.01-1.05 compared with water at 20 ℃, the ion exchanger is amorphous oxygen-1.05, the ion exchanger is one of 2-octyl-4-isothiazolin-3-one, the ion exchanger is one of a neutral particle size (D50) of 30-70 nm, the ionic synthetic silica salt with relative thermal decomposition of an amphoteric oxygen ion, the ionic nano-alkyl chloride, the ionic stabilizing agent is one of a synergistic agent with a trace element, the ionic silicon dioxide, the ionic stabilizing agent when the ionic silicon dioxide is a molecular weight of 100-7-9 ℃, the ionic nano boron-7-9 ℃, the ionic stabilizing agent is one of an amphoteric ion type industrial silicon dioxide, the ionic nano-3-ethylene carbonate, the ionic stabilizing agent, the ionic silicon dioxide is one of an amphoteric carbon dioxide with the ionic type, the ionic type of the ionic type industrial silicon dioxide, the ionic type of the ionic type, the ionic type industrial silicon dioxide, the ionic type of.

10. The preparation method of a novel long-acting broad-spectrum antibacterial multifunctional water-based architectural coating according to any one of claims 1 to 8, wherein the preparation of the water-based nano-composite antibacterial agent adopted in the method comprises the following steps:

in a pressure-reducing and pressure-resistant reaction vessel capable of stirring, heating, cooling, dropwise adding, replacing with nitrogen, pressurizing by using nitrogen and using a vacuum pump, adding deionized water accounting for 10-15% of the total mass of the deionized water into a dispersion reaction mixing kettle according to the mass percentage of the formula, then adding isothiazolinone, and dissolving at the rotating speed of 600-800 rmp to prepare isothiazolinone solution for later use;

under the protection of nitrogen, sequentially adding deionized water accounting for 15-20% of the total mass into a dispersion reaction mixing kettle at the temperature of 0 +/-15 ℃, sequentially adding silver particles, zinc oxide and titanium dioxide, uniformly stirring at the rotating speed of 200-300 rmp by magnetic stirring to prepare composite nano powder slurry, vacuumizing, filling nitrogen, and sealing for later use;

under the protection of nitrogen, adding deionized water, an ion exchanger and a penetrating agent which account for 15-20% of the total mass ratio at the temperature of 25 +/-5 ℃, and stirring at the rotating speed of 800-1200 rpm for 10-15 min; cooling to 0 +/-10 ℃, adding the composite nano powder slurry, magnetically stirring at the rotation speed of 200-300 rpm under the reduced pressure of 0.6-1.3 kpa, keeping the temperature and stirring for 10-15 min, heating to 90-110 ℃, keeping the temperature constant, and carrying out heat treatment reaction for 1.5-2.5 hr while stirring;

under the protection of nitrogen, dropwise adding the synergistic agent from a burette, stirring with a magnetic stirrer while dropwise adding until the powder is completely suspended, stopping the machine when the M value of the volume percentage of the liquid mixture is measured to be 40-60, dehydrating the mixture for 2-2.5 hours while stirring at low speed under the reduced pressure of 0.6-1.3 kpa, and stopping stirring when the water content is measured to be 2-3;

under the protection of nitrogen, cooling to 25 +/-5 ℃, adding the rest deionized water, the plant extract and the isothiazolinone solution sequentially at the beginning, wherein the dropping speed is 3-5L/min, then heating to 25-40 ℃, beginning to drop the solubilizing stabilizer, stirring at the rotating speed of 300-500 rpm by magnetic force after dropping at the speed of 20-30 drops/min is finished, keeping the temperature constant, continuing to stir for reaction for 1.5-2 hr, and then cooling to the normal temperature to obtain the aqueous nano composite antibacterial agent.