WO2023029272A1

WO2023029272A1 - Antibacterial material

Info

Publication number: WO2023029272A1
Application number: PCT/CN2021/135961
Authority: WO
Inventors: 王淑敏; 张晓婷; 高红荣; 胡晓璐; 于洋
Original assignee: 歌尔股份有限公司
Priority date: 2021-08-31
Filing date: 2021-12-07
Publication date: 2023-03-09
Also published as: CN113637312A

Abstract

The present invention provides an antibacterial material. The antibacterial material comprises a resin base material, an additive, and a carboxylated carbon nanotube-loaded silver-coated hollow glass microsphere composite material. The additive and the carboxylated carbon nanotube-loaded silver-coated hollow glass microsphere composite material are added into the resin base material. The present invention provides a functional material having low density, high heat dissipation performance, and antibacterial properties.

Description

an antibacterial material

technical field

The invention relates to the field of polymer materials, more specifically, the invention relates to an antibacterial material.

Background technique

Resin materials are widely used in electronic products. Resin materials have the characteristics of high strength and good temperature resistance. However, such materials have high density and are not suitable for the development trend of lightweight and high heat dissipation.

In order to achieve light weight and high heat dissipation, it is usually modified by adding low-density inorganic lightweight materials to the resin material. However, the method of adding low-density inorganic lightweight fillers will decrease the toughness of the material while reducing the density and improving the heat dissipation, resulting in a significant decrease in the impact strength of the material. In addition, nowadays, people's awareness of antibacterial health care in the living environment is gradually increasing. In electronic products and some application fields, materials are required to have certain antibacterial properties, so that they can be kept clean and sterile for a long time during use, and avoid harmful microorganisms. breed.

Contents of the invention

The purpose of the present invention is to provide a new technical solution for antibacterial materials.

According to one aspect of the present invention, an antibacterial material is provided. The antibacterial material includes a resin base material, an additive, and a carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material, and the additive and the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material are added to the In the above resin substrate.

Optionally, the resin substrate includes polycarbonate, polypropylene, polyethylene, polyamide, polybutylene terephthalate, polyethylene terephthalate, polysulfone, polyether ether ketone , any one of acrylonitrile-butadiene-styrene or an alloy material of at least two of the above materials.

Optionally, the additive includes at least one of an antioxidant, a compatibilizer, a coupling agent, a light stabilizer, a lubricant and a reinforcing agent.

Optionally, the compatibilizer includes at least one of maleic anhydride grafted acrylonitrile-styrene polymer, polypropylene grafted maleic anhydride and maleic anhydride grafted ethylene-octene copolymer;

The coupling agent is a silane coupling agent;

Described lubricant is calcium stearate;

The reinforcing agent is talcum powder.

Optionally, for the antibacterial material, in terms of parts by mass, the resin substrate is 62 to 89 parts, the additive is 6 to 18 parts, and the carboxylated carbon nanotube-loaded hollow glass microspheres are loaded with silver Composite materials are 5 to 15 parts.

Optionally, the preparation method of the carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material comprises:

S101, mixing hollow glass microspheres with methanol, an aqueous solution of silver nitrate and polyvinylpyrrolidone;

S102, adding an aqueous solution of sodium borohydride to the liquid obtained in step S101, and mixing;

S103, adding ammonia water to the liquid obtained in step S102 to obtain an amino-modified hollow glass microsphere silver-loaded antibacterial agent;

S104, adding the surface carboxylated carbon nanotubes into ethylene glycol and dispersing them evenly;

S105. Add the amino-modified hollow glass microsphere silver-loaded antibacterial agent to the liquid obtained in step S104, and radiate heating, so that the carboxyl groups on the surface of the carboxylated carbon nanotubes and the amino-modified hollow glass Amino groups on the surface of microbead-loaded silver antimicrobial agent undergo amidation reaction.

Optionally, the mass ratio of the surface carboxylated carbon nanotubes to the amino-modified hollow glass microsphere-loaded silver antibacterial agent is 1˜2:1.

Optionally, the preparation method of the surface carboxylated carbon nanotubes comprises:

Mix concentrated sulfuric acid and concentrated nitric acid to obtain a mixed solution;

Adding carbon nanotubes into the mixed solution to perform an activation reaction;

Wherein, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1:3, the reaction temperature is 40°C-60°C, and the reaction time is 3h-5h.

Optionally, the volume ratio of the methanol to the silver nitrate aqueous solution is 2:1, and the concentration of the ammonia water is 6 mol/L.

Optionally, in the step S104:

Surface carboxylated carbon nanotubes are dispersed in ethylene glycol by ultrasonic dispersion;

Wherein, the surface carboxylated carbon nanotube accounts for 2%-10% of the total mass of the surface carboxylated carbon nanotube and the ethylene glycol.

In the embodiment of the present disclosure, the resin substrate is modified under the condition of adding carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material, so that the modified resin material has the characteristics of light weight and low density while increasing heat dissipation performance. , and also has antibacterial function and good impact strength.

Other features of the present invention and advantages thereof will become apparent from the following detailed description of exemplary embodiments of the present invention with reference to the accompanying drawings.

Description of drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention.

Fig. 1 is the flowchart of the preparation method of the antibacterial material provided by the embodiment of the present disclosure;

2 is a flow chart for the preparation of surface carboxylated carbon nanotubes provided by an embodiment of the present disclosure;

Fig. 3 is a flow chart of the preparation of the amino-modified hollow glass microsphere-loaded silver antibacterial agent provided by the embodiment of the present disclosure.

Detailed ways

Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that the relative arrangements of components and steps, numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise.

The following description of at least one exemplary embodiment is merely illustrative in nature and in no way taken as limiting the invention, its application or uses.

Techniques, methods and devices known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, such techniques, methods and devices should be considered part of the description.

In all examples shown and discussed herein, any specific values should be construed as exemplary only, and not as limitations. Therefore, other instances of the exemplary embodiment may have different values.

It should be noted that like numerals and letters denote like items in the following figures, therefore, once an item is defined in one figure, it does not require further discussion in subsequent figures.

An embodiment of the present disclosure provides an antibacterial material, which includes a resin substrate, an additive, and a carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material, the additive and the carboxylated carbon nanotube-loaded hollow glass microsphere A silver loaded composite is added to the resin matrix.

The resin base material has the characteristics of high strength and excellent temperature resistance.

Hollow glass microspheres belong to inorganic non-metallic materials, which are usually nano-, micro- or micro-nano-scale inorganic material balls, forming a hollow structure inside. Hollow glass microspheres have the characteristics of light weight and good thermal stability.

Hollow glass microspheres are a kind of lightweight material with excellent performance, which can reduce the weight of the resin substrate and achieve the effect of lightening the material when it is applied in the solution of the present disclosure.

For example, the material of the hollow glass microspheres is silicon dioxide, aluminum oxide, zirconium oxide, magnesium oxide, sodium silicate and the like.

After the hollow glass microspheres are loaded with silver, the hollow glass microspheres can be endowed with antibacterial and antibacterial effects.

Carbon nanotubes (CNTs) have good elasticity, fatigue resistance and isotropy, and their hardness is very high, comparable to that of diamond, and they also have good flexibility and can be stretched. Moreover, carbon nanotubes have good heat transfer performance. Carbon nanotubes have a very large aspect ratio, so their heat exchange performance along the length direction is high, and their heat exchange performance in the vertical direction is relatively low. Through proper orientation, carbon nanotubes can be synthesized with high anisotropy thermally conductive material. Carbon nanotubes have high thermal conductivity, as long as a small amount of carbon nanotubes are doped in the material, the thermal conductivity of the material will be greatly improved.

In the embodiment of the present disclosure, the resin substrate is modified under the condition of adding carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material, so that the modified resin material has light weight and low density while increasing heat dissipation performance. Features (that is, lightweight), and also has antibacterial function and good impact strength.

The antibacterial material provided by the embodiments of the present disclosure can be applied to the field of electronic products.

Wherein, the resin base material is, for example, a thermoplastic resin material.

In some examples of the present disclosure, the resin substrate includes polycarbonate, polypropylene, polyethylene, polyamide, polybutylene terephthalate, polyethylene terephthalate, polysulfone, Any one of polyetheretherketone, acrylonitrile-butadiene-styrene, or an alloy material of at least two of the above materials.

In the embodiments of the present disclosure, the additives are added to the resin base material and mixed evenly, which can be used to improve the temperature resistance, durability and other properties of the material, depending on the type of the additives.

For example, the additive includes at least one of antioxidant, compatibilizer, coupling agent, light stabilizer, lubricant and reinforcing agent.

Wherein, the compatibilizer is, for example, a maleic anhydride grafted compatibilizer.

The maleic anhydride graft compatibilizer makes the material have high polarity and reactivity by introducing a strong polar reactive group, which can greatly improve the compatibility and dispersion of the composite material, and help to make the carboxylation The carbon nanotube-loaded hollow glass microsphere-loaded silver composite material is uniformly dispersed in the resin base material.

In some examples of the present disclosure, the compatibilizer includes at least one of maleic anhydride grafted acrylonitrile-styrene polymer, polypropylene grafted maleic anhydride and maleic anhydride grafted ethylene-octene copolymer kind.

Adding an antioxidant to the resin base material can prevent thermal oxidation degradation of the material in the long-term aging process.

In some examples of the present disclosure, the antioxidant is antioxidant 1010 (chemical name: tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester).

Antioxidant 1010 is a phenolic antioxidant. After it is applied to the resin substrate, it can improve the oxidation resistance of the material and effectively extend the service life of the resin product. Moreover, the antioxidant 1010 has low volatility, high thermal stability, long-lasting effect, no pollution, and non-toxicity.

Wherein, the coupling agent is, for example, a silane coupling agent, such as silane coupling agent KH550.

For another example, the coupling agent is KH792.

Adding the silane coupling agent into the resin substrate can improve the dispersion and adhesion of the filler in the resin, and improve the compatibility between the inorganic filler and the resin.

Wherein, the lubricant is, for example, calcium stearate.

Described calcium stearate has excellent lubricating performance, and it can be used as lubricant and release agent.

Wherein, the reinforcing agent is talcum powder.

Wherein, the model of the light stabilizer is 944.

In the existing related technologies, the weight reduction of resin materials is usually achieved by adding micro-foaming. However, the micro-foaming method will reduce the mechanical properties of the resin material, and the process is complicated, and bubble control is a technical problem.

In the scheme of the present disclosure, the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material with low density, high heat dissipation and antibacterial properties is used, combined with additives and then mixed with the resin substrate, to prepare a lightweight, low- Density, high heat dissipation and antibacterial modified resin material. Moreover, the prepared material can meet the mechanical properties of the material while achieving light weight, and has good impact strength.

For the antibacterial material provided by the embodiments of the present disclosure, in terms of parts by mass, the resin base material is 62-89 parts, the additive is 6-18 parts, and the carboxylated carbon nanotube-loaded hollow glass microbeads-loaded silver composite The material is 5-15 parts. Wherein, the material of the resin base material is the material listed above, and the specific type of the additive can be flexibly selected according to specific conditions. The resin substrate can be modified by adding the carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material, which has the characteristics of light weight while increasing the heat dissipation performance of the resin substrate, and also has antibacterial properties. Function.

In an embodiment of the present disclosure, as shown in Figures 2 and 3, the preparation method of the carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material includes:

S101, mixing hollow glass microspheres with methanol, an aqueous solution of silver nitrate and polyvinylpyrrolidone.

The consumption of the methanol and the silver nitrate depends on the consumption of the hollow glass microspheres.

In some examples of the present disclosure, the volume ratio of the methanol to the silver nitrate aqueous solution is 2:1.

The silver nitrate is a silver source.

The polyvinylpyrrolidone (polyvinyl pyrrolidone, PVP) is a non-ionic polymer compound, belonging to N-vinylamide polymers, which contains

group, here as a dispersant.

In some examples of the present disclosure, 500 mg of the hollow glass microspheres (for example, a particle size of 10 μm to 250 μm) are mixed with 20 ml of the methanol, 10 ml of the aqueous solution of silver nitrate and an appropriate amount of polyvinylpyrrolidone PVP, And avoid light and stir for 6h.

S102, adding an aqueous solution of sodium borohydride to the liquid obtained in step S101, and mixing.

Wherein, the aqueous solution of sodium borohydride was slowly dropped into the liquid obtained through the step S101 at a uniform speed, and the reaction was stirred slowly for 30 minutes to fully proceed the reaction.

Sodium borohydride is an inorganic substance with the chemical formula NaBH ₄ , which is used as a reducing agent. Sodium borohydride is easily soluble in methanol.

S103. Add ammonia water to the liquid obtained in step S102 to obtain an amino-modified hollow glass microsphere-loaded silver antibacterial agent.

Wherein, the concentration of ammonia water is controlled to be 6 mol/L, for example.

After adding ammonia water to the liquid obtained in step S102, continue to stir and react for 10 minutes, then centrifuge, settle, wash and dry, and finally obtain an amino-modified hollow glass microsphere-loaded silver antibacterial agent.

Taking the 500 mg hollow microspheres in the above step S101 as an example, the concentration of the ammonia water is 6 mol/L, and the amount of ammonia water added is, for example, 5 ml to 10 ml.

S104, adding the surface carboxylated carbon nanotubes into ethylene glycol and dispersing them evenly.

Wherein, the preparation method of the carbon nanotube of described surface carboxylation comprises:

It should be noted that the concentrated sulfuric acid refers to sulfuric acid with a concentration of 98% and above, and the concentrated nitric acid refers to nitric acid with a concentration of 63% and above.

In said S104 step:

Wherein, the mass ratio of the surface carboxylated carbon nanotubes to the amino-modified hollow glass microsphere-loaded silver antibacterial agent is 1-2:1.

The carboxyl group on the surface of the carbon nanotube and the amino group on the surface of the hollow glass microsphere silver-loaded antibacterial agent undergo an amidation reaction by using a microwave method and heating by thermal radiation, as follows:

The carboxyl group on the surface of the carbon nanotube and the amino group on the surface of the hollow glass microbead-loaded silver antibacterial agent undergo an amidation reaction by adopting a microwave method and radiating heating, so as to prepare a carbon nanotube-loaded glass microbead-loaded silver composite material. The problems of uneven mixing, weight loss, heat dissipation and antibacterial effects in the mixing of the three fillers are improved.

According to a second embodiment of the present disclosure, a method for preparing the above-mentioned resin material is provided, which includes: as shown in Figure 1, adding carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite materials and additives to the resin In the substrate, and stir evenly, and then granulate.

In some examples of the present disclosure, the mixture formed by carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material, additives and resin substrate is added to the high mixer, wherein, in terms of parts by mass, the The resin substrate is 62 to 89 parts, the additive is 6 to 18 parts, and the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material is 5 to 15 parts. After mixing evenly, the extrusion temperature is Under the condition of 270°C, use a twin-screw extruder to extrude and granulate.

The preparation process of the present disclosure is simple, low in cost and easy in large-scale production.

The antibacterial material prepared by the present disclosure modifies the resin substrate by adding carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material, so that the modified resin material has light weight and low density while increasing heat dissipation performance The characteristics (that is, lightweight), and also have antibacterial function and maintain good mechanical properties.

Example 1

An antibacterial material, comprising a resin substrate, an additive and a carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material, the additive and the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material are added to In the resin substrate, wherein, the resin substrate is polycarbonate and is 89 parts, the carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material is 5 parts, and the additive includes 1.5 parts of anti- Oxygen agent 1010, 2.5 parts of maleic anhydride grafted acrylonitrile-styrene polymer and 2 parts of silane coupling agent KH550.

Example 2

An antibacterial material, comprising a resin substrate, an additive and a carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material, the additive and the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material are added to In the resin base material, wherein, the resin base material is polycarbonate and is 84 parts, and the carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material is 10 parts, and the additive includes 1.5 parts of anti- Oxygen agent 1010, 2.5 parts of maleic anhydride grafted acrylonitrile-styrene polymer and 2 parts of silane coupling agent KH550.

Example 3

An antibacterial material, comprising a resin substrate, an additive and a carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material, the additive and the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material are added to In the resin substrate, wherein, the resin substrate is polycarbonate and is 79 parts, the carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material is 15 parts, and the additive includes 1.5 parts of anti- Oxygen agent 1010, 2.5 parts of maleic anhydride grafted acrylonitrile-styrene polymer and 2 parts of silane coupling agent KH550.

The above-mentioned embodiment 1 to embodiment 3 are low density and high heat dissipation antibacterial polycarbonate resin materials.

Comparative example 1

A kind of resin material, comprises resin base material and additive, and described additive is added in described resin base material, and wherein, described resin base material is polycarbonate and is 94 parts, and described additive comprises 1.5 parts of antioxidant 1010, 2.5 parts of maleic anhydride grafted acrylonitrile-styrene polymer and 2 parts of silane coupling agent KH550.

In Comparative Example 1, no carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material was added.

Embodiment 1～embodiment 3, and the processing technology of comparative example 1 are as follows:

Add the mixture into a high-speed mixer, and after mixing evenly, extrude and granulate with a twin-screw extruder under the condition that the extrusion temperature is 270°C.

Example 4

An antibacterial material, comprising a resin substrate, an additive and a carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material, the additive and the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material are added to In the resin substrate, wherein, the resin substrate is PA6 polyamide and is 77 parts, the carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material is 5 parts, and the additive includes 1 part of light Stabilizer 944, 2 parts of antioxidant 1010, 6 parts of polypropylene grafted maleic anhydride (PP-g-MAH), 7 parts of maleic anhydride grafted ethylene-octene copolymer and 2 parts of silane coupling agent KH550.

Example 5

An antibacterial material, comprising a resin substrate, an additive and a carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material, the additive and the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material are added to In the resin substrate, wherein, the resin substrate is PA6 polyamide and is 72 parts, the carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material is 10 parts, and the additive includes 1 part of light Stabilizer 944, 2 parts of antioxidant 1010, 6 parts of polypropylene grafted maleic anhydride (PP-g-MAH), 7 parts of maleic anhydride grafted ethylene-octene copolymer and 2 parts of silane coupling agent KH550.

Example 6

An antibacterial material, comprising a resin substrate, an additive and a carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material, the additive and the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material are added to In the resin substrate, wherein, the resin substrate is PA6 polyamide and is 67 parts, the carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material is 15 parts, and the additive includes 1 part of light Stabilizer 944, 2 parts of antioxidant 1010, 6 parts of polypropylene grafted maleic anhydride (PP-g-MAH), 7 parts of maleic anhydride grafted ethylene-octene copolymer and 2 parts of silane coupling agent KH550.

The above-mentioned embodiments 4 to 6 are low-density, high-radiation antibacterial PA6 polyamide resin materials.

Comparative example 2

A kind of resin material, comprises resin substrate and additive, and described additive is added in described resin substrate, and wherein, described resin substrate is PA6 polyamide and is 82 parts, and described additive includes 1 part of light stabilizer 944, 2 parts of antioxidant 1010, 6 parts of polypropylene grafted maleic anhydride (PP-g-MAH), 7 parts of maleic anhydride grafted ethylene-octene copolymer and 2 parts of silane coupling agent KH550.

In Comparative Example 2, no carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material was added.

Embodiment 4～embodiment 6, and the processing technology of comparative example 2 are as follows:

Add the mixture into a high mixer, and after mixing evenly, extrude and granulate with a twin-screw extruder under the condition that the extrusion temperature is 275°C.

Example 7

An antibacterial material, comprising a resin substrate, an additive and a carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material, the additive and the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material are added to In the resin substrate, wherein, the resin substrate is polypropylene and is 84 parts, the carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material is 5 parts, and the additive includes 1 part of antioxidant Agent 1010, 1 part of calcium stearate, 5 parts of talc, 2 parts of polypropylene grafted maleic anhydride (PP-g-MAH) and 2 parts of coupling agent KH792.

Example 8

An antibacterial material, comprising a resin substrate, an additive and a carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material, the additive and the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material are added to In the resin substrate, wherein, the resin substrate is polypropylene and is 79 parts, the carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material is 10 parts, and the additive includes 1 part of antioxidant Agent 1010, 1 part of calcium stearate, 5 parts of talc, 2 parts of polypropylene grafted maleic anhydride (PP-g-MAH) and 2 parts of coupling agent KH792.

Example 9

An antibacterial material, comprising a resin substrate, an additive and a carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material, the additive and the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material are added to In the resin base material, wherein, the resin base material is polypropylene and is 74 parts, the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material is 15 parts, and the additive includes 1 part of antioxidant Agent 1010, 1 part of calcium stearate, 5 parts of talc, 2 parts of polypropylene grafted maleic anhydride (PP-g-MAH) and 2 parts of coupling agent KH792.

The above-mentioned embodiments 7 to 9 are low-density and high-radiation antibacterial polypropylene resin materials.

Comparative example 3

A kind of resin material, comprises resin substrate and additive, and described additive is added in described resin substrate, and wherein, described resin substrate is polypropylene and is 89 parts, and described additive includes 1 part of antioxidant 1010 , 1 part of calcium stearate, 5 parts of talc, 2 parts of polypropylene grafted maleic anhydride (PP-g-MAH) and 2 parts of coupling agent KH792.

In Comparative Example 3, no carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material was added.

Embodiment 7～embodiment 9, and the processing technology of comparative example 3 are as follows:

Add the mixture into a high mixer, and after mixing evenly, extrude and granulate with a twin-screw extruder under the condition that the extrusion temperature is 200°C.

Table 1 shows the densities, mechanical properties and antibacterial properties of the products of Examples 1 to 9 and the products of Comparative Examples 1 to 3.

Table 1

Among them, the detection method of the inhibition rate of Escherichia coli and Staphylococcus aureus is as follows:

1. Prepare at least 3 antibacterial materials in each embodiment as test pieces. Prepare at least 6 pieces of materials without antibacterial ingredients, that is, materials in each comparative example, as samples, 3 samples without added antibacterial ingredients are used to measure the number of live bacteria immediately after inoculation, and the other 3 pieces are used to measure the number of inoculated bacteria. The number of live bacteria after 24h.

2. Each sample is made into a disc with a diameter of 40 mm and a thickness of 5 mm. Put the samples into sterile Petri dishes respectively, with the test side facing up. 0.4 ml of the inoculum solution was sucked up with a pipette, and dropped onto the surface of each sample. Cover the inoculated bacteria solution with a pre-prepared film with a diameter of 35 mm, and gently press the film downward to spread the bacteria solution around and ensure that the bacteria solution does not overflow from the edge of the film. After the samples were inoculated and covered with film, the Petri dish was covered again.

3. Place the culture dish at 35°C and 90% humidity for cultivation. For samples that do not contain antibacterial ingredients, measure the number of bacteria immediately after inoculation, and count the viable bacteria after 24 hours for the remaining samples.

Bacterial inhibition rate=1-(viable bacteria/total bacteria)*100

After the carboxylated carbon nanotube-loaded hollow glass microbeads-loaded silver composite material is modified, the density of the resin material is significantly reduced, and the notched impact strength is also maintained at a good level, which can meet the structural strength requirements of the product. At the same time, the heat dissipation and The antibacterial property showed a clear increasing trend.

Referring to the standard QBT2591-2003, the antibacterial rate ≥ 99% can be reported as having a strong antibacterial effect, and the antibacterial plastic with an antibacterial rate ≥ 90% can be reported to have an antibacterial effect. The antibacterial product of the present disclosure has a bacteriostatic rate of more than 99.9% for Escherichia coli and a bacteriostatic rate of more than 99.9% for Staphylococcus aureus, and has a strong antibacterial effect. Although some specific embodiments of the present invention have been described in detail through examples, those skilled in the art should understand that the above examples are for illustration only and not intended to limit the scope of the present invention. Those skilled in the art will appreciate that modifications can be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.

Claims

An antibacterial material, characterized in that it includes a resin substrate, an additive, and a carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material, and the additive and the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite Materials are added to the resin matrix.
antibacterial material according to claim 1, is characterized in that, described resin substrate comprises polycarbonate, polypropylene, polyethylene, polyamide, polybutylene terephthalate, polyethylene terephthalate Any one of alcohol ester, polysulfone, polyether ether ketone, acrylonitrile-butadiene-styrene or an alloy material of at least two of the above materials.
The antibacterial material according to claim 1, wherein the additive includes at least one of an antioxidant, a compatibilizer, a coupling agent, a light stabilizer, a lubricant and a reinforcing agent.
antibacterial material according to claim 3, is characterized in that, described compatibilizer comprises maleic anhydride grafted acrylonitrile-styrene polymer, polypropylene grafted maleic anhydride and maleic anhydride grafted ethylene-octene at least one of copolymers;

The coupling agent is a silane coupling agent;

Described lubricant is calcium stearate;

The reinforcing agent is talcum powder.
The antibacterial material according to claim 1, characterized in that, in terms of parts by mass, the resin substrate is 62 to 89 parts, the additive is 6 to 18 parts, and the carboxylated carbon nanotube-loaded hollow glass The microbead-loaded silver composite material is 5-15 parts.
antibacterial material according to claim 1, is characterized in that, the preparation method of described carboxylated carbon nanotube loaded hollow glass microspheres silver-loaded composite material comprises:

S101, mixing hollow glass microspheres with methanol, an aqueous solution of silver nitrate and polyvinylpyrrolidone;

S102, adding an aqueous solution of sodium borohydride to the liquid obtained in step S101, and mixing;

S103, adding ammonia water to the liquid obtained in step S102 to obtain an amino-modified hollow glass microsphere silver-loaded antibacterial agent;

S104, adding the surface carboxylated carbon nanotubes into ethylene glycol and dispersing them evenly;

S105. Add the amino-modified hollow glass microsphere silver-loaded antibacterial agent to the liquid obtained in step S104, and radiate heating, so that the carboxyl groups on the surface of the carboxylated carbon nanotubes and the amino-modified hollow glass Amino groups on the surface of microbead-loaded silver antimicrobial agent undergo amidation reaction.
The antibacterial material according to claim 6, characterized in that the mass ratio of the surface carboxylated carbon nanotubes to the amino-modified hollow glass microsphere-loaded silver antibacterial agent is 1-2:1.
antibacterial material according to claim 6, is characterized in that, the preparation method of the carbon nanotube of described surface carboxylation comprises:

Mix concentrated sulfuric acid and concentrated nitric acid to obtain a mixed solution;

Adding carbon nanotubes into the mixed solution to perform an activation reaction;

Wherein, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1:3, the reaction temperature is 40°C-60°C, and the reaction time is 3h-5h.
The antibacterial material according to claim 6, wherein the volume ratio of the methanol to the silver nitrate aqueous solution is 2:1, and the concentration of the ammonia water is 6mol/L.
antibacterial material according to claim 6, is characterized in that, in described S104 step:

Surface carboxylated carbon nanotubes are dispersed in ethylene glycol by ultrasonic dispersion;

Wherein, the surface carboxylated carbon nanotube accounts for 2%-10% of the total mass of the surface carboxylated carbon nanotube and the ethylene glycol.