阅读说明：本技术 一种耐久高活性抗菌抗病毒剂及其应用 (Durable high-activity antibacterial antiviral agent and application thereof ) 是由 陈广川 于红光 尹珊珊 于 2021-10-25 设计创作，主要内容包括：本发明涉及抗菌材料技术领域,具体涉及一种耐久高活性抗菌抗病毒剂及其应用,由以下质量份数的原料制备而成：抗菌抗病毒有效成分1-15份、有机溶剂50-70份、成膜剂20-50份、固化剂1-5份、香精1-5份。本发明所制备的抗菌抗病毒剂抗菌率及抗病毒率均达到99％以上同时具有优良的耐久性,无VOC气体挥发等优点。(The invention relates to the technical field of antibacterial materials, in particular to a durable high-activity antibacterial antiviral agent and application thereof, wherein the durable high-activity antibacterial antiviral agent is prepared from the following raw materials in parts by mass: 1-15 parts of antibacterial and antiviral active ingredient, 50-70 parts of organic solvent, 20-50 parts of film forming agent, 1-5 parts of curing agent and 1-5 parts of essence. The antibacterial and antiviral agent prepared by the invention has the antibacterial rate and the antiviral rate of over 99 percent, and has the advantages of excellent durability, no VOC gas volatilization and the like.)

1. The durable high-activity antibacterial antiviral agent is characterized in that the antiviral agent is a spray and is prepared from the following raw materials in parts by mass: 1-15 parts of antibacterial and antiviral active ingredient, 50-70 parts of organic solvent, 20-50 parts of film forming agent, 1-5 parts of curing agent and 1-5 parts of essence.

2. The durable highly active antibacterial and antiviral agent according to claim 1, wherein said effective antibacterial and antiviral ingredient is one or more of silicone modified quaternary ammonium salt, nano silver solution, nano inorganic antibacterial particles, chitosan and natural plant extract.

3. The durable highly active antibacterial and antiviral agent according to claim 2, wherein said nano inorganic antibacterial particles are one or more of nano titanium dioxide, zinc oxide, bismuth tungstate, bismuth molybdate, and have a particle size of 5-40 nm.

4. The durable highly-active antibacterial and antiviral agent according to claim 2, wherein said plant in said natural plant extract is one or more of aloe, astragalus, forsythia, pomegranate rind, mugwort, and isatis root.

5. The durable highly active antibacterial and antiviral agent according to claim 1, wherein said curing agent is an aqueous isocyanate curing agent; the organic solvent is one of ethanol, propylene glycol methyl ether acetate and propylene glycol methyl ether.

6. The durable highly active antibacterial and antiviral agent according to claim 1, wherein said film forming agent is an aqueous self-drying film forming resin comprising one or more of acrylic resin, hydroxyacrylic resin, polyurethane resin, silicone resin and polyvinyl alcohol.

7. The durable highly active antibacterial and antiviral agent according to claim 1, wherein the mass ratio of the organic solvent to the film forming agent is 3: 1.

8. The durable highly active antibacterial and antiviral agent according to claim 1, wherein said nanosilver solution is prepared by the following method:

weighing a certain amount of silver nitrate to prepare 0.001mol/L aqueous solution;

adding NaOH solution, and adjusting the pH value of silver nitrate solution to 8;

preparing a sodium citrate solution with the mass fraction of 1%;

and gradually heating the 50ml of silver nitrate solution to boiling, slowly adding 5ml of 1% sodium citrate solution, stirring for 30min after dropwise addition, removing a heat source, and cooling the liquid to room temperature to obtain the nano-silver solution.

9. The durable highly active antibacterial/antiviral agent according to claim 1, wherein said plant extract is prepared by the following method:

cleaning plant, soaking in distilled water for 20min, and decocting with slow fire to 70-80 deg.C;

covering the solution for 20min, and filtering to obtain corresponding plant extractive solution.

10. Use of the durable highly active antibacterial and antiviral agent according to any one of claims 1 to 9 for antibacterial and antiviral treatment of glass, plastic, tile, wood or metal surfaces.

Technical Field

The invention relates to the technical field of antibacterial materials, and particularly relates to a durable high-activity antibacterial antiviral agent and application thereof.

Background

With the improvement of modern life quality of people, people pay more and more attention to air quality and living environment, especially people pay more attention to health and sanitation environment since new crown epidemic situation, and various antibacterial and antiviral agents are generated.

CN111528222A discloses an antibacterial and antiviral nano-zinc oxide spray, which mainly comprises nano-zinc oxide, dispersion liquid, aldehyde removing agent, wetting agent, antifreeze, penetrant and deionized water, but the patent does not describe antibacterial property, antiviral property and durability.

CN109287626A and CN109463380A disclose a slow-release long-acting antibacterial spray, which mainly comprises silver ion doped bismuth tungstate nanoparticles, water glass, film forming assistant, anti-aging agent, emulsifier, ethanol and deionized water, but the spray needs to be heated and cured after being sprayed, which greatly limits the application range and is not beneficial to popularization.

CN108077311A discloses an anti-haze antibacterial spray, which mainly comprises a composite ion antibacterial material, a film forming agent, a thickening agent, nano titanium dioxide, a plant extractant, a preservative, a solubilizer, a freshener and deionized water, but the spray contains inorganic nano particles, and white particles are easy to appear on the surface of the spray and the substrate to affect the beauty of objects, thereby limiting the application range. Therefore, it is not easy to develop a durable highly active antibacterial antiviral agent that can solve the above-mentioned drawbacks.

Disclosure of Invention

Aiming at the characteristics of low antibacterial rate and antiviral rate, poor durability and the like of the existing antibacterial antiviral agent, the durable high-activity antibacterial antiviral agent is prepared, and the antibacterial rate and the antiviral rate of the prepared antibacterial antiviral agent both reach more than 99 percent and have the advantages of excellent durability, no VOC gas volatilization and the like.

The technical scheme provided by the invention is as follows:

the durable high-activity antibacterial antiviral agent is a spray and is prepared from the following raw materials in parts by mass: 1-15 parts of antibacterial and antiviral active ingredient, 50-70 parts of organic solvent, 20-50 parts of film forming agent, 1-5 parts of curing agent and 1-5 parts of essence.

The antibacterial and antiviral active ingredient is one or more of organosilicon modified quaternary ammonium salt, nano silver solution, nano inorganic antibacterial particles, chitosan and natural plant extract;

the nano inorganic antibacterial particles are one or more of nano titanium dioxide, zinc oxide, bismuth tungstate and bismuth molybdate, and the particle size of the nano inorganic antibacterial particles is between 5 and 40 nm;

the preparation method of the nano silver solution comprises the following steps:

s1, weighing a certain amount of silver nitrate to prepare 0.001mol/L aqueous solution;

s2, adding NaOH solution, and adjusting the pH value of the silver nitrate solution to 8;

s3, preparing a sodium citrate solution with the mass fraction of 1%;

s4: and gradually heating the 50ml of silver nitrate solution to boiling, slowly adding 5ml of 1% sodium citrate solution, stirring for 30min after dropwise addition, removing a heat source, and cooling the liquid to room temperature to obtain the nano-silver solution.

The molecular weight of the chitosan is 5-50 ten thousand, and the deacetylation degree is more than 85;

the plant in the natural plant extracting solution is one or more of aloe, astragalus, fructus forsythiae, pomegranate rind, mugwort and radix isatidis;

the preparation method of the plant extract comprises the following steps:

s1, cleaning the plants, adding distilled water, soaking for 20min, and boiling with slow fire to 70-80 deg.C;

s2, sealing the solution for 20min, and filtering to obtain corresponding plant extractive solution.

The organosilicon modified quaternary ammonium salt is HM-5540, Guangzhou Jianice Limited.

The organic solvent is one of ethanol, propylene glycol methyl ether acetate (PMA) and propylene glycol methyl ether (PM);

the film forming agent is water-based self-drying film forming resin and comprises one or more of acrylic resin, hydroxy acrylic resin, polyurethane resin, organic silicon resin and polyvinyl alcohol;

the curing agent is a water-based isocyanate curing agent;

the essence is water-soluble industrial essence, and the specific fragrance type is customized according to the requirements of customers;

preferably, the mass ratio of the organic solvent to the film forming agent is 3: 1.

The durable high-activity antibacterial and antiviral agent prepared by the invention is mainly applied to antibacterial and antiviral treatment on the surfaces of glass, plastics, ceramic tiles, wood boards, metals and other solids;

the antibacterial antiviral agent is sprayed on the surface of an object by 20-30cm away from the surface of the object, and the spraying amount is controlled to be 10-30 square meters per L.

Advantageous effects

The durable high-activity antibacterial antiviral agent prepared by the invention mainly has the following advantages:

1. according to the disinfection technical specification, the antiviral activity rate of the coronavirus GX-P2V is more than or equal to 99 percent;

2. according to the technical specification for disinfection, the suspension sterilization test of the antiviral agent is carried out, and the antibacterial rate of escherichia coli and staphylococcus aureus is more than or equal to 99 percent;

the self-drying time is less than or equal to 30 minutes at the room temperature of 3.25 ℃, the special proportion of the modified resin and the environment-friendly solvent in the formula ensures good film-forming property and has good self-drying property, the film-forming property and the self-drying property are balanced by optimizing the proportion of the organic solvent and the film-forming agent, so that the film layer has good film-forming property and self-drying property, and the antiviral agent can form a uniform antiviral film layer with good binding force and hardness on the surface of an object without baking after being sprayed on the surface of the object;

4. the used raw materials have no volatilization of VOC organic pollutants;

5. the specific proportion of the curing agent and the film forming agent in the formula synergistically enhances the binding force of the antiviral film layer, and meanwhile, the good leveling property of the resin enables the formed film layer to have excellent compactness, and the film layer firmness time is more than or equal to 6 months as tested by a laboratory accelerated aging experiment, so that the antiviral performance is not remarkably reduced;

6. natural green active ingredients and an environment-friendly solvent are adopted as raw materials;

7. high temperature resistance (no change after boiling in water at 80 ℃ for 24 hours);

8. acid, alkali and salt resistance (the film layer is intact and can not be damaged after being soaked in salt solution with pH 4, pH 12 and 20% for 24 h).

Detailed Description

Example 1

The durable high-activity antibacterial antiviral agent is a spray and is prepared from the following raw materials in parts by mass: 8 parts of antibacterial and antiviral active ingredients, 60 parts of organic solvent, 20 parts of film-forming agent, 3 parts of curing agent and 3 parts of essence.

The antibacterial and antiviral active ingredient is one or more of organosilicon modified quaternary ammonium salt, nano silver solution, nano inorganic antibacterial particles, chitosan and natural plant extract;

the nano inorganic antibacterial particles are one or more of nano titanium dioxide, zinc oxide, bismuth tungstate and bismuth molybdate, and the particle size of the nano inorganic antibacterial particles is between 5 and 40 nm;

the preparation method of the nano silver solution comprises the following steps:

s1, weighing a certain amount of silver nitrate to prepare 0.001mol/L aqueous solution;

s2, adding NaOH solution, and adjusting the pH value of the silver nitrate solution to 8;

s3, preparing a sodium citrate solution with the mass fraction of 1%;

s4: and gradually heating the 50ml of silver nitrate solution to boiling, slowly adding 5ml of 1% sodium citrate solution, stirring for 30min after dropwise addition, removing a heat source, and cooling the liquid to room temperature to obtain the nano-silver solution.

The molecular weight of the chitosan is 5-50 ten thousand, and the deacetylation degree is more than 85;

the plant in the natural plant extracting solution is one or more of aloe, astragalus, fructus forsythiae, pomegranate rind, mugwort and radix isatidis;

the preparation method of the plant extract comprises the following steps:

s1, cleaning the plants, adding distilled water, soaking for 20min, and boiling with slow fire to 70-80 deg.C;

s2, sealing the solution for 20min, and filtering to obtain corresponding plant extractive solution.

The organosilicon modified quaternary ammonium salt is HM-5540, Guangzhou Jianice Limited.

The organic solvent is one of ethanol, propylene glycol methyl ether acetate (PMA) and propylene glycol methyl ether (PM);

the film forming agent is water-based self-drying film forming resin and comprises one or more of acrylic resin, hydroxy acrylic resin, polyurethane resin, organic silicon resin and polyvinyl alcohol;

the curing agent is a water-based isocyanate curing agent;

the essence is water-soluble industrial essence, and the specific fragrance type is customized according to the requirements of customers;

preferably, the mass ratio of the organic solvent to the film forming agent is 3: 1.

Example 2

The durable high-activity antibacterial antiviral agent is a spray and is prepared from the following raw materials in parts by mass: 1 part of antibacterial and antiviral active ingredient, 65 parts of organic solvent, 30 parts of film-forming agent, 1 part of curing agent and 5 parts of essence.

The antibacterial and antiviral active ingredient is one or more of organosilicon modified quaternary ammonium salt, nano silver solution, nano inorganic antibacterial particles, chitosan and natural plant extract;

the nano inorganic antibacterial particles are one or more of nano titanium dioxide, zinc oxide, bismuth tungstate and bismuth molybdate, and the particle size of the nano inorganic antibacterial particles is between 5 and 40 nm;

the preparation method of the nano silver solution comprises the following steps:

s1, weighing a certain amount of silver nitrate to prepare 0.001mol/L aqueous solution;

s2, adding NaOH solution, and adjusting the pH value of the silver nitrate solution to 8;

s3, preparing a sodium citrate solution with the mass fraction of 1%;

s4: and gradually heating the 50ml of silver nitrate solution to boiling, slowly adding 5ml of 1% sodium citrate solution, stirring for 30min after dropwise addition, removing a heat source, and cooling the liquid to room temperature to obtain the nano-silver solution.

The molecular weight of the chitosan is 5-50 ten thousand, and the deacetylation degree is more than 85;

the plant in the natural plant extracting solution is one or more of aloe, astragalus, fructus forsythiae, pomegranate rind, mugwort and radix isatidis;

the preparation method of the plant extract comprises the following steps:

s1, cleaning the plants, adding distilled water, soaking for 20min, and boiling with slow fire to 70-80 deg.C;

s2, sealing the solution for 20min, and filtering to obtain corresponding plant extractive solution.

The organosilicon modified quaternary ammonium salt is HM-5540, Guangzhou Jianice Limited.

The organic solvent is one of ethanol, propylene glycol methyl ether acetate (PMA) and propylene glycol methyl ether (PM);

the film forming agent is water-based self-drying film forming resin and comprises one or more of acrylic resin, hydroxy acrylic resin, polyurethane resin, organic silicon resin and polyvinyl alcohol;

the curing agent is a water-based isocyanate curing agent;

the essence is water-soluble industrial essence, and the specific fragrance type is customized according to the requirements of customers;

example 3

The durable high-activity antibacterial antiviral agent is a spray and is prepared from the following raw materials in parts by mass: 15 parts of antibacterial and antiviral active ingredient, 70 parts of organic solvent, 50 parts of film-forming agent, 1 part of curing agent and 1 part of essence.

The antibacterial and antiviral active ingredient is one or more of organosilicon modified quaternary ammonium salt, nano silver solution, nano inorganic antibacterial particles, chitosan and natural plant extract;

the nano inorganic antibacterial particles are one or more of nano titanium dioxide, zinc oxide, bismuth tungstate and bismuth molybdate, and the particle size of the nano inorganic antibacterial particles is between 5 and 40 nm;

the preparation method of the nano silver solution comprises the following steps:

s1, weighing a certain amount of silver nitrate to prepare 0.001mol/L aqueous solution;

s2, adding NaOH solution, and adjusting the pH value of the silver nitrate solution to 8;

s3, preparing a sodium citrate solution with the mass fraction of 1%;

s4: and gradually heating the 50ml of silver nitrate solution to boiling, slowly adding 5ml of 1% sodium citrate solution, stirring for 30min after dropwise addition, removing a heat source, and cooling the liquid to room temperature to obtain the nano-silver solution.

The molecular weight of the chitosan is 5-50 ten thousand, and the deacetylation degree is more than 85;

the plant in the natural plant extracting solution is one or more of aloe, astragalus, fructus forsythiae, pomegranate rind, mugwort and radix isatidis;

the preparation method of the plant extract comprises the following steps:

s1, cleaning the plants, adding distilled water, soaking for 20min, and boiling with slow fire to 70-80 deg.C;

s2, sealing the solution for 20min, and filtering to obtain corresponding plant extractive solution.

The organosilicon modified quaternary ammonium salt is HM-5540, Guangzhou Jianice Limited.

The organic solvent is one of ethanol, propylene glycol methyl ether acetate (PMA) and propylene glycol methyl ether (PM);

the film forming agent is water-based self-drying film forming resin and comprises one or more of acrylic resin, hydroxy acrylic resin, polyurethane resin, organic silicon resin and polyvinyl alcohol;

the curing agent is a water-based isocyanate curing agent;

the essence is water-soluble industrial essence, and the specific fragrance type is customized according to the requirements of customers;

example 4

The durable high-activity antibacterial antiviral agent is a spray and is prepared from the following raw materials in parts by mass: 10 parts of antibacterial and antiviral active ingredients, 50 parts of organic solvent, 40 parts of film-forming agent, 5 parts of curing agent and 5 parts of essence.

The antibacterial and antiviral active ingredient is one or more of organosilicon modified quaternary ammonium salt, nano silver solution, nano inorganic antibacterial particles, chitosan and natural plant extract;

the nano inorganic antibacterial particles are one or more of nano titanium dioxide, zinc oxide, bismuth tungstate and bismuth molybdate, and the particle size of the nano inorganic antibacterial particles is between 5 and 40 nm;

the preparation method of the nano silver solution comprises the following steps:

s1, weighing a certain amount of silver nitrate to prepare 0.001mol/L aqueous solution;

s2, adding NaOH solution, and adjusting the pH value of the silver nitrate solution to 8;

s3, preparing a sodium citrate solution with the mass fraction of 1%;

s4: and gradually heating the 50ml of silver nitrate solution to boiling, slowly adding 5ml of 1% sodium citrate solution, stirring for 30min after dropwise addition, removing a heat source, and cooling the liquid to room temperature to obtain the nano-silver solution.

The molecular weight of the chitosan is 5-50 ten thousand, and the deacetylation degree is more than 85;

the plant in the natural plant extracting solution is one or more of aloe, astragalus, fructus forsythiae, pomegranate rind, mugwort and radix isatidis;

the preparation method of the plant extract comprises the following steps:

s1, cleaning the plants, adding distilled water, soaking for 20min, and boiling with slow fire to 70-80 deg.C;

s2, sealing the solution for 20min, and filtering to obtain corresponding plant extractive solution.

The organosilicon modified quaternary ammonium salt is HM-5540, Guangzhou Jianice Limited.

The organic solvent is one of ethanol, propylene glycol methyl ether acetate (PMA) and propylene glycol methyl ether (PM);

the film forming agent is water-based self-drying film forming resin and comprises one or more of acrylic resin, hydroxy acrylic resin, polyurethane resin, organic silicon resin and polyvinyl alcohol;

the curing agent is a water-based isocyanate curing agent;

the essence is water-soluble industrial essence, and the specific fragrance type is customized according to the requirements of customers;

example 5

The durable high-activity antibacterial antiviral agent is a spray and is prepared from the following raw materials in parts by mass: 5 parts of antibacterial and antiviral active ingredients, 55 parts of organic solvent, 35 parts of film-forming agent, 2 parts of curing agent and 3 parts of essence.

The antibacterial and antiviral active ingredient is one or more of organosilicon modified quaternary ammonium salt, nano silver solution, nano inorganic antibacterial particles, chitosan and natural plant extract;

the nano inorganic antibacterial particles are one or more of nano titanium dioxide, zinc oxide, bismuth tungstate and bismuth molybdate, and the particle size of the nano inorganic antibacterial particles is between 5 and 40 nm;

the preparation method of the nano silver solution comprises the following steps:

s1, weighing a certain amount of silver nitrate to prepare 0.001mol/L aqueous solution;

s2, adding NaOH solution, and adjusting the pH value of the silver nitrate solution to 8;

s3, preparing a sodium citrate solution with the mass fraction of 1%;

s4: and gradually heating the 50ml of silver nitrate solution to boiling, slowly adding 5ml of 1% sodium citrate solution, stirring for 30min after dropwise addition, removing a heat source, and cooling the liquid to room temperature to obtain the nano-silver solution.

The molecular weight of the chitosan is 5-50 ten thousand, and the deacetylation degree is more than 85;

the plant in the natural plant extracting solution is one or more of aloe, astragalus, fructus forsythiae, pomegranate rind, mugwort and radix isatidis;

the preparation method of the plant extract comprises the following steps:

s1, cleaning the plants, adding distilled water, soaking for 20min, and boiling with slow fire to 70-80 deg.C;

s2, sealing the solution for 20min, and filtering to obtain corresponding plant extractive solution.

The organosilicon modified quaternary ammonium salt is HM-5540, Guangzhou Jianice Limited.

The organic solvent is one of ethanol, propylene glycol methyl ether acetate (PMA) and propylene glycol methyl ether (PM);

the film forming agent is water-based self-drying film forming resin and comprises one or more of acrylic resin, hydroxy acrylic resin, polyurethane resin, organic silicon resin and polyvinyl alcohol;

the curing agent is a water-based isocyanate curing agent;

the essence is water-soluble industrial essence, and the specific fragrance type is customized according to the requirements of customers;

comparative example 1

This comparative example provides a durable highly active antibacterial/antiviral agent, which is identical to example 1 except that the antibacterial/antiviral active ingredient is not added to the raw materials.

Comparative example 2

This comparative example provides a durable, highly active anti-bacterial antiviral agent, which is identical to that of example 1 except that no film-forming agent is added to the raw materials.

Comparative example 3

This comparative example provides a durable highly active antibacterial/antiviral agent, which was prepared under the same conditions as in example 1 except that no curing agent was added to the raw materials.

Comparative example 4

This comparative example provides a durable highly active antibacterial antiviral agent, and the conditions are exactly the same as in example 1 except that the raw material ratio is different. The comparative example comprises the following raw materials in parts by mass: 8 parts of antibacterial and antiviral active ingredients, 60 parts of organic solvent, 10 parts of film-forming agent, 3 parts of curing agent and 3 parts of essence.

Comparative example 5

This comparative example provides a durable highly active antibacterial antiviral agent, and the conditions are exactly the same as in example 1 except that the raw material ratio is different. The comparative example comprises the following raw materials in parts by mass: 8 parts of antibacterial and antiviral active ingredients, 60 parts of organic solvent, 60 parts of film-forming agent, 3 parts of curing agent and 3 parts of essence.

The antiviral agents in the above examples and comparative examples are sprayed on the metal surface, and the spraying amount is controlled to be 60-90 square meters per liter. After the film layer is dried after spraying, the following performance tests are carried out: the antiviral activity rate to coronavirus GX-P2V, the antibacterial rate to escherichia coli and staphylococcus aureus, and the corrosion resistance, hardness and adhesion of an antiviral agent film layer;

the antiviral agents in the above examples and comparative examples were respectively sprayed on metal surfaces, and the spraying amount was controlled to be 20 square meters per liter. After the spraying, the film layer is dried, boiled in water at 80 ℃ for 24h, soaked in salt solution with pH 4, pH 12 and 20% for 24h, and then the antiviral activity rate of the film layer on coronavirus GX-P2V is detected.

The antiviral agents in the above examples and comparative examples were respectively sprayed on metal surfaces, and the spraying amount was controlled to be 20 square meters per liter. After the spraying, the film layer is dried, boiled in water at 80 ℃ for 24h, soaked in salt solution with pH 4, pH 12 and 20% for 24h, and then the antibacterial rate of the film layer to escherichia coli is detected.

The antiviral agents in the above examples and comparative examples were respectively sprayed on metal surfaces, and the spraying amount was controlled to be 20 square meters per liter. After the spraying, the film layer is dried, boiled in water at 80 ℃ for 24h, soaked in salt solution with pH 4, pH 12 and 20% for 24h, and then the antibacterial rate of the film layer on staphylococcus aureus is detected.