1. An antibacterial coating material, characterized by comprising the following components by mass: 0.1-0.5 parts by mass of silver-loaded modified rGO, 10-15 parts by mass of a functional polymer and 80-90 parts by mass of water; the silver-loaded modified rGO comprises a modified rGO and silver particles loaded on the modified rGO in situ, wherein the modified rGO is prepared by modifying graphene oxide with a modified material and then reducing the modified graphene oxide, and the modified material is at least one of ethylenediamine and polyethyleneimine; the functional polymer is a polymer containing a functional group capable of reacting with a carboxyl group or a hydroxyl group.

2. The antibacterial coating material according to claim 1, wherein the graphene oxide has a sheet diameter of 2-50 μm and a thickness of 0.8-1.2 nm.

3. The antibacterial coating material of claim 1, wherein the functional polymer is at least one selected from polyethylene glycol, acrylic polyurethane, waterborne polyurethane and hyperbranched polyurethane prepolymer containing-NCO.

4. The antibacterial coating material according to any one of claims 1 to 3, characterized in that the antibacterial coating material further comprises 0.2 to 0.5 parts by mass of an auxiliary agent.

5. The antibacterial coating material according to claim 4, wherein the auxiliary agent is at least one of an antifoaming agent and a leveling agent.

6. A method for preparing an antibacterial coating material according to any one of claims 1 to 5, characterized by comprising the steps of:

dispersing graphene oxide in water, adding the modified material and a silver source, uniformly mixing, heating at 80 ℃, adding a reducing agent for reaction, and separating solids after reaction to obtain silver-loaded modified rGO;

and mixing the silver-loaded modified rGO, the functionalized polymer and water to obtain the antibacterial coating material.

7. The method of preparing the antimicrobial coating material of claim 6, wherein the silver-loaded modified rGO is prepared by: dispersing 0.1-0.4 part by mass of graphene oxide in 200-1000 parts by mass of water, adding 1.8-11 parts by mass of a modification material, stirring for 0.5-1 h, adding 0.05-0.25 part by mass of a silver source, stirring for 2-8 h, heating for 5-15 min, adding 0.5-1.5 parts by mass of a reducing agent, stirring for 1-2 h, filtering, washing, and freeze-drying to obtain the silver-loaded modified rGO.

8. The method for preparing an antibacterial coating material according to claim 6, wherein the reducing agent is at least one selected from sodium citrate, glucose, and L-ascorbic acid.

9. An antibacterial coating, characterized in that the antibacterial coating is prepared from the antibacterial coating material of any one of claims 1-5 by baking at 60-80 ℃.

10. An article comprising a substrate and a coating on the substrate, wherein the coating is the antimicrobial coating of claim 9.

Background

People pay special attention to the sanitation of living home environment, traffic environment and public medical facility space, the demand for antibacterial materials is sharply increased, an 'all-round healthy automobile' becomes a new development direction of the automobile industry, and along with the continuous development of public health career, novel antibacterial medical equipment and antibacterial medical infrastructure are built to become necessary of antibacterial medical basic equipment. With the development of antibacterial materials, the antibacterial fabric is particularly applied to home textiles and antibacterial household appliances, and products such as antibacterial refrigerators and antibacterial washing machines are successively released. Zeolite-based inorganic antibacterial agents Zeomic carrying silver metal ions abroad such as japan are widely used for decorative panels, automobile steering wheels. B6000, Silvatur of Dow, Basff, Germany^TM930 the antibacterial product is an aqueous environment-friendly product, is safe and stable, and has an obvious antibacterial effect. The domestic antibacterial coating material is mainly prepared by mixing simple antibacterial agents, has the defects of short antibacterial aging of organic antibacterial agents, poor dispersibility of inorganic antibacterial agents, poor single antibacterial agent effect and the like, does not have obvious antibacterial effect and short duration, and therefore, the development of a novel water-based antibacterial coating material becomes the key for solving the problems.

Disclosure of Invention

In view of the above, there is a need to provide an antibacterial coating material, a preparation method thereof, an antibacterial coating and an article thereof, which can solve the above technical problems.

The first aspect of the application provides an antibacterial coating material, which comprises the following components, by mass, 0.1-0.5 part of silver-loaded modified rGO, 10-15 parts of a functional polymer and 80-90 parts of water; the silver-loaded modified rGO comprises a modified rGO and silver particles loaded on the modified rGO in situ, wherein the modified rGO is prepared by modifying graphene oxide with a modified material and then reducing the modified graphene oxide, and the modified material is at least one of ethylenediamine and polyethyleneimine; the functional polymer is a polymer containing a functional group capable of reacting with a carboxyl group or a hydroxyl group.

The antibacterial coating material provided by the embodiment of the application utilizes amino groups in the modified material and the surface of graphene oxideA large number of carboxyl (-COOH), epoxy (-O-) and hydroxyl (-OH) groups are combined, increasing the bonding with Ag⁺The binding site for can load more silver granules on the modified rGO that forms, and then promote antibacterial effect, unreacted carboxyl and hydroxyl can carry out chemical grafting with the functional group in the functional polymer on the silver-carrying modified rGO that forms, thereby combine polymer and inorganic silver-carrying modified rGO, overcome the not good defect of single type antibacterial agent effect. The application discloses antibacterial coating material is water based paint, uses water as the solvent, and green utilizes graphite alkene "nanometer sword" physical contact and absorption parcel bacterium, and the silver granule of load can produce active oxygen free radical, and oxidative stress kills the bacterium, has better antibiotic effect.

According to some embodiments of the present application, the graphene oxide has a plate diameter of 2-50 μm and a thickness of 0.8-1.2nm, and the graphene oxide is easily dispersed, provides relatively more sites, and is beneficial to Ag⁺Adsorption and fixation, and is more beneficial to cutting bacteria, and the antibacterial property is improved.

According to some embodiments of the present disclosure, the functional polymer is at least one selected from the group consisting of polyethylene glycol, acrylic polyurethane, aqueous polyurethane, and hyperbranched polyurethane prepolymer containing — NCO. Functional groups such as-NCO groups or double bonds in the selected functional polymer can be chemically grafted with unreduced carboxyl or hydroxyl on the silver-loaded modified rGO, so that organic polymers and inorganic silver-loaded materials are combined together.

According to some embodiments of the present application, the antibacterial coating material further comprises 0.2 to 0.5 parts by mass of an auxiliary.

According to some embodiments of the present application, the auxiliary agent is at least one of a defoamer and a leveling agent.

In a second aspect, the present application provides a method for preparing the above antibacterial coating material, comprising the following steps:

dispersing graphene oxide in water, adding the modified material and a silver source, uniformly mixing, heating at 80 ℃, adding a reducing agent for reaction, and separating solids after reaction to obtain silver-loaded modified rGO;

and mixing the silver-loaded modified rGO, the functionalized polymer and water to obtain the antibacterial coating material.

According to the preparation method provided by the embodiment of the application, the used graphene oxide has a large number of carboxyl, epoxy and hydroxyl, and can be combined with amino in a modified material, so that Ag is added⁺Binding sites of Ag from a silver source⁺Through the combination of electrostatic adsorption and amino, carboxyl, epoxy and hydroxyl, the modified graphene oxide is fixed on the surface of graphene oxide, and the Ag can be ensured by uniformly mixing and heating the graphene oxide, the modified material and a silver source⁺Fully adsorbing with a carrier, and then adding a reducing agent to enable the graphene oxide and the adsorbed Ag combined with the modified material⁺Synchronously carrying out reduction reaction and adsorbed Ag⁺The prepared silver-loaded modified rGO is stable in property and has an antibacterial effect, carboxyl and hydroxyl which are not reduced on the surface of the modified rGO can be chemically grafted with functional groups in functional polymers, the stability of a coating material is further improved, the long-acting performance is excellent, the antibacterial coating material prepared by the preparation method is a water-based coating, the antibacterial effect is good, the coating can be formed by curing at a lower temperature, and the preparation method has a better application prospect in the fields of automotive interior coatings, medical instruments, antibacterial home textiles and the like.

According to some embodiments of the present application, the silver-loaded modified rGO is prepared by: dispersing 0.1-0.4 part by mass of graphene oxide in 200-1000 parts by mass of water, adding 1.8-11 parts by mass of a modification material, stirring for 0.5-1 h, adding 0.05-0.25 part by mass of a silver source, stirring for 2-8 h, heating for 5-15 min, adding 0.5-1.5 parts by mass of a reducing agent, stirring for 1-2 h, filtering, washing, and freeze-drying to obtain the silver-loaded modified rGO.

According to some embodiments of the present application, the reducing agent is selected from at least one of sodium citrate, glucose, L-ascorbic acid.

According to some embodiments of the present application, the silver source is silver nitrate.

The third aspect of the application provides an antibacterial coating, wherein the antibacterial coating is prepared by baking the antibacterial coating material at 60-80 ℃.

In a fourth aspect, the present application provides an article comprising a substrate and a coating overlying the substrate, wherein the coating is the antimicrobial coating described above.

According to some embodiments of the present application, the coating is applied to the substrate by any one of spraying, dipping, wiping.

Drawings

FIG. 1 is a photograph showing the inhibition of Escherichia coli, Staphylococcus aureus and Candida albicans by the antibacterial coating materials obtained in examples 1 and 2.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

An embodiment of the present application provides an antibacterial coating material comprising the following components by mass: 0.1-0.5 part by mass of silver-loaded modified rGO, 10-15 parts by mass of a functional polymer and 80-90 parts by mass of water.

In this application, rGO refers to reduced graphene oxide. The silver-loaded modified rGO comprises modified rGO and silver particles loaded on the modified rGO in situ. The modified rGO is prepared by modifying graphene oxide with a modified material and then reducing the modified graphene oxide. The modified material is at least one of ethylenediamine and polyethyleneimine. The functional polymer is a polymer containing a functional group capable of reacting with a carboxyl group or a hydroxyl group.

According to the antibacterial coating material provided by the embodiment of the application, amino groups in the modified material are combined with a large number of carboxyl (-COOH), epoxy (-O-) and hydroxyl (-OH) groups on the surface of graphene oxide, so that the content of Ag in the modified material is increased⁺The binding site for can load more silver granules on the modified rGO that forms, and then promote antibacterial effect, unreacted carboxyl and hydroxyl can carry out chemical grafting with the functional group in the functional polymer on the silver-carrying modified rGO that forms, thereby combine polymer and inorganic silver-carrying modified rGO, overcome the not good defect of single type antibacterial agent effect. The application discloses antibacterial coating material is water based paint, uses water as the solvent, and green utilizes graphite alkene "nanometer sword" physical contact and absorption parcel bacterium, and the silver granule of load can produce active oxygen free radical, and oxidative stress kills the bacterium, has better antibiotic effect.

In some embodiments, the graphene oxide has a sheet diameter of 2 to 50 μm and a thickness of 0.8 to 1.2 nm.

In some embodiments, the functional polymer is at least one selected from the group consisting of polyethylene glycol, acrylic polyurethane, aqueous polyurethane, and hyperbranched polyurethane prepolymer containing-NCO. Functional groups such as-NCO groups or double bonds of the functional macromolecules can be chemically grafted with unreduced carboxyl or hydroxyl on the silver-loaded modified rGO, so that the organic macromolecules and the inorganic silver-loaded materials are combined together.

In some embodiments, the composition further comprises 0.2-0.5 parts by mass of an auxiliary agent. The auxiliary agent can be selected from defoaming agent, leveling agent, etc.

The embodiment of the application also provides a preparation method of the antibacterial coating material, which comprises the following steps:

dispersing graphene oxide in water, adding the modified material and a silver source, uniformly mixing, heating at 80 ℃, adding a reducing agent for reaction, and separating solids after reaction to obtain silver-loaded modified rGO;

and mixing the silver-loaded modified rGO, the functionalized polymer and water to obtain the antibacterial coating material.

According to the preparation method provided by the embodiment of the application, the used graphene oxide has a large number of carboxyl, epoxy and hydroxyl, and can be combined with amino in a modified material, so that Ag is added⁺Binding sites of Ag from a silver source⁺Through the combination of electrostatic adsorption and amino, carboxyl, epoxy and hydroxyl, the modified graphene oxide is fixed on the surface of graphene oxide, and the Ag can be ensured by uniformly mixing and heating the graphene oxide, the modified material and a silver source⁺Fully adsorbing with a carrier, and then adding a reducing agent to enable the graphene oxide and the adsorbed Ag combined with the modified material⁺Synchronously carrying out reduction reaction and adsorbed Ag⁺The prepared silver-loaded modified rGO is stable in property and has an antibacterial effect, carboxyl and hydroxyl which are not reduced on the surface of the modified rGO can be chemically grafted with functional groups in functional polymers, the stability of a coating material is further improved, the long-acting performance is excellent, the antibacterial coating material prepared by the preparation method is a water-based coating, the antibacterial effect is good, the coating can be formed by curing at a lower temperature, and the preparation method has a better application prospect in the fields of automotive interior coatings, medical instruments, antibacterial home textiles and the like.

In some embodiments, the silver-loaded modified rGO is prepared by: dispersing 0.1-0.4 part by mass of graphene oxide in 200-1000 parts by mass of water, adding 1.8-11 parts by mass of a modification material, stirring for 0.5-1 h, adding 0.05-0.25 part by mass of a silver source, stirring for 2-8 h, heating for 5-15 min, adding 0.5-1.5 parts by mass of a reducing agent, stirring for 1-2 h, filtering, washing, and freeze-drying to obtain the silver-loaded modified rGO.

In some embodiments, the reducing agent is selected from at least one of sodium citrate, glucose, L-ascorbic acid.

In some embodiments, the silver source is silver nitrate.

The embodiment of the application also provides an antibacterial coating, which is prepared by baking the antibacterial coating material at 60-80 ℃.

The embodiment of the application also provides an article, which comprises a substrate and a coating covering the substrate, wherein the coating is the antibacterial coating. The coating can be coated on the substrate by any one of spraying, dipping and wiping.

The effects of the present application will be described below with reference to specific examples.

Example 1

Adopting 0.1g of graphene oxide, pouring into 200mL of water to prepare graphene oxide dispersion, adding 6mL of ethylenediamine, stirring for 1h, adding 0.05g of silver nitrate solid, stirring for 6h, heating for 10min at 80 ℃ by using a microwave oven, adding 0.6g of glucose, stirring for 1h, filtering the solution, washing for 3-4 times by using deionized water to obtain silver-loaded modified rGO, and freeze-drying the silver-loaded modified rGO.

0.2g of prepared silver-loaded modified rGO, 20g of anisotropic acid ester terminated waterborne polyurethane, 80g of distilled water and 0.2g of defoaming agent are uniformly mixed to obtain the antibacterial coating material.

And spraying the obtained antibacterial coating material on a substrate, and baking at the low temperature of 60-80 ℃ to obtain the water-based antibacterial coating.

Example 2

Adopting 0.3g of graphene oxide, pouring into 800mL of water to prepare graphene dispersion, adding 4mL of polyethyleneimine, stirring for 0.5h, adding 0.2g of silver nitrate solid, stirring for 8h, heating for 15min at 80 ℃ by using a microwave oven, adding 1.5g of glucose, stirring for 2h, filtering the solution, washing for 3-4 times by using deionized water to obtain silver-loaded modified rGO, and freeze-drying the silver-loaded modified rGO.

And uniformly mixing 0.3g of prepared silver-loaded modified rGO, 28g of acrylic polyurethane, 85g of distilled water and 0.5g of defoaming agent to obtain the antibacterial coating material.

And (3) coating the obtained antibacterial coating material on a substrate by dipping, and baking at the low temperature of 60-80 ℃ to obtain the water-based antibacterial coating.

The antibacterial coating materials obtained in example 1 and example 2 were used as test samples to perform an antibacterial test. A blank control sample is set in the antibacterial experiment, and the antibacterial effects on escherichia coli, staphylococcus aureus and candida albicans are respectively measured. The experimental results are shown in fig. 1, in which (a) shows the results of the test for escherichia coli, (B) shows the results of the test for staphylococcus aureus, and (c) shows the results of the test for candida albicans, in which a shows the sample of the antibacterial coating material in example 1, and B shows the sample of the antibacterial coating material in example 2. The experimental results show that the antibacterial coating materials provided in the embodiments 1 and 2 have good antibacterial performance on escherichia coli, staphylococcus aureus and candida albicans. The table 1 shows the antibacterial effect data of the antibacterial coating material in the example 1 on different strains, and it can be seen from the table that the antibacterial coating material provided by the application has higher bacteriostatic action on plant bacillus, staphylococcus aureus and candida albicans, and the bacteriostatic rate is up to more than 99%.

TABLE 1 antibacterial effect of the antibacterial coating material of example 1 against various bacterial species

Although the present invention has been described with reference to the above preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.