CN111841165A - A kind of manufacturing method of antibacterial disinfection air filter material - Google Patents

Abstract

The present invention provides a method for manufacturing an antibacterial and disinfecting air filter material, which comprises: (S1) dissolving water-based polyurethane in a solvent to obtain a mixed solution; (S2) adding silver-loaded graphene to the mixed solution to form a spinning silk liquid; (S3) electrospinning with the spinning liquid to form an electrospinning non-woven fabric; the electrospinning non-woven fabric includes water-based polyurethane fibers, and the interior of the water-based polyurethane fibers is mixed with silver-loaded graphene; (S4) in Surface deposition of electrospun nonwoven fabrics to prepare _TiO2 thin films. In the electrospinning non-woven fabric, after absorbing the water vapor in the air, the surface of the water-based polyurethane fiber softens into a gel-like substance, which not only allows the water-based polyurethane fiber to better adhere to the particles in the air, but also makes the water-based polyurethane fiber. The silver-loaded graphene in it is easier to contact with microorganisms in the air, and plays a role in antibacterial and disinfection. Water can also make a small amount of silver into silver ions, inactivating the microorganisms it comes into contact with, further enhancing the disinfection and antibacterial effect.

Description

A kind of manufacturing method of antibacterial disinfection air filter material

technical field

The invention relates to the field of functional textiles, in particular to a method for manufacturing an antibacterial and disinfecting air filter material.

Background technique

In the stage of accelerated world industrialization, industrial exhaust gas and automobile exhaust have caused huge harm to the global air environment, and have also caused a great threat to human health. After inhaling seriously polluted air, the metabolism of the human body is affected, which accelerates human aging, and brings various chronic diseases to the respiratory system, and also induces various cancers. In the period of high virus incidence, the filter material with bactericidal effect plays an important role for personnel, especially medical staff, which can effectively prevent cross infection and protect their own health.

As an air filter material, the main consideration is its filtration efficiency and filtration resistance. On the one hand, the high filtration efficiency can intercept more particles and play a better protective effect on the human body; on the other hand, the lower filtration resistance can increase the use time without affecting breathing, and can also prevent secondary pollution.

How to achieve the barrier of tiny particles, the most important means is to reduce the gap of fibers, while ordinary fiber material products usually have relatively large gaps, which can reach hundreds of microns. If you want to achieve the same filtering effect, the finished product will become thick. For microfibers, there are currently two methods for mass-producing microfibers.

Meltblown method. The technology is to form a melt by melting thermoplastic polymers (polyester, polypropylene, etc.) under heat, and spray them out at high speed through small spinneret holes, and the high-speed airflow draws the fibers with hot air. The filaments are stretched to the limit, and then rapidly cooled by cold air to shape the fibers. Chinese patent: CN201810698720.8 discloses a method for generating tourmaline-modified non-woven air filter material by melt-blown method, which achieves high efficiency and low resistance filtering effect; Chinese patent: CN201410235944.7 discloses a polypropylene agricultural biological Nonwoven fabric and method of making the same. The problem of repelling insects and light transmission is solved, and the cost is reduced. However, this method is not suitable for materials with low thermal evaporation temperature.

Electrospinning. The technology is that the electrospinning technology uses the electrostatic voltage generated by a high-voltage electrostatic device to draw the spinning solution into ultra-fine fibers under the action of an electric field. Because of the unique technological advantage of electrospinning, nano-scale fibers can be obtained, and the advantages of the obtained fibers are high porosity, good air permeability, good pore connectivity, and small pore size, which are very suitable for air purification composites. filter material. Chinese patent: CN201611213539.0 discloses a nanofiber membrane for filtering an infusion filter and a preparation method thereof, which can precisely control the pore size and satisfy the filtering effect of different infusion liquids. Chinese patent: CN201610784058.9 discloses a high-efficiency and low-resistance electrospinning nanofiber air filter material and a batch preparation method, which achieves the effect of stable filtration performance and batch production.

Silver-loaded graphene can destroy the bacterial cell wall and cause the dissolution of cell contents, hinder the synthesis of enzymes that are beneficial to bacterial metabolism, and destroy the synthesis of DNA, so that the bacteria lose their biological activity and complete the sterilization process. Chinese patent: CN201210397566.3 discloses a film packaging material with antistatic and antibacterial properties and a preparation method thereof. The synergistic effect of silver-loaded graphene is used to achieve antibacterial effect; Chinese patent: N201510431869.6 discloses a The invention discloses a preparation method of a polymer-based silver-loaded graphene nanometer antibacterial material, and prepares an antibacterial material that can be applied to the electronic and electrical industry, the automobile industry, the instrumentation industry, the machinery industry and the building material industry.

Nano-anatase TiO2 can utilize a series of redox reactions generated by visible light catalysis to degrade a variety of microorganisms, including viruses, spores, bacteria and protozoa. Chinese patent: CN201310073600.6 discloses a visible light nanometer titanium dioxide photocatalytic sterilization and purification solid powder coating, which can kill germs and inhibit mildew; Chinese patent: CN106561710B discloses a kind of titanium dioxide sol that can degrade pesticide residues and its preparation The method utilizes the photocatalytic action of titanium dioxide to achieve the functions of degrading sterilization and degrading pesticide residues.

There are two most direct methods for combining nano-anatase TiO2 with fabrics: electron beam evaporation, vapor deposition and magnetron sputtering.

Electron beam evaporation is to heat electrons to bombard the coating material, and the kinetic energy of the electrons is converted into heat energy, so that the target material is heated to evaporate and form a film. Suitable for evaporating high melting point metals or compounds, Chinese patent: CN103924198A discloses a method for preparing graphene conductive film by electron beam evaporation, Chinese patent: CN102169944B discloses a light-emitting diode with Ag/ITO/zinc oxide-based composite transparent electrode and its preparation method. On the level of mature equipment application technology, people have also made great innovation and progress. Chinese patent: CN102492924A discloses a free ion bombardment-assisted electron beam evaporation equipment and a coating method using the same, which solves the problem between the film layers. The problem of low bonding force, Chinese patent: CN104611682A discloses a double-sided reciprocating continuous coating magnetron sputtering winding coating machine, which improves the efficiency, simplifies the machine, and reduces the floor space. However, for many compounds, the method of electron beam evaporation will cause it to be decomposed by heat, so this method is not suitable.

Chemical vapor deposition technology is a process that uses gaseous substances to produce chemical reactions and transport reactions on solids and generate solid deposits. This technology first forms volatile substances through chemical reactions, and then transfers the above substances to the deposition area. A chemical reaction is produced on the solid and a solid substance is produced. Chinese patent: CN101381080B discloses a method for directly preparing a carbon nanotube composite conductive agent. Weigh LaNiO 2 grams of catalyst and 20 grams of Super P, and use a high-speed mixer to mix the two evenly As a catalyst, a mixture of CH4/H2 (volume ratio 40/100) of 80L per hour was used as the raw material gas, and the mixture was reacted at 700°C for 1 hour in a fixed bed reactor to obtain a mixture of carbon nanotubes and Super P containing catalyst. The most basic chemical vapor deposition reactions include thermal decomposition reactions, chemical synthesis reactions, and chemical transport reactions, and most of the thermal decomposition temperatures are around 600 °C, which is not suitable for fabric-based film preparation.

Magnetron sputtering means that electrons collide with argon atoms in the process of flying to the substrate under the action of an electric field, and the argon atoms generate Ar ions and new electrons. A large number of target atoms are shot out, and neutral target atoms are deposited on the substrate. Using magnetron sputtering technology to sputter a layer of film on the surface of the fabric, it is easy to obtain a functional film. Chinese patent: CN106637590B discloses a high light transmission heat insulation fabric and its manufacturing method, Chinese patent: CN102779988B discloses a A modification method for the coating of composite negative electrode materials for lithium ion batteries is widely used in industries such as solar cells and semiconductors. Chinese patent: CN102779988B discloses a method for modifying the coating of composite negative electrode materials for lithium ion batteries, and Chinese patent: CN103280498B discloses a The invention discloses a preparation method of a tapered zinc oxide/nickel oxide heterojunction diode. Magnetron sputtering coating has high deposition efficiency and high repeatability, and can continuously and efficiently obtain thin films with uniform thickness, which is easy for industrial operation.

To sum up, the shortcomings of the sterilization filter materials on the market today are: usually the filtration effect is not high or the thickness is large, and there is no sterilization effect.

SUMMARY OF THE INVENTION

In view of the defects in the prior art, the object of the present invention is to provide a method for producing an antibacterial and disinfecting air filter material, which adopts water-based polyurethane fibers and mixes silver-loaded graphene, which can also be antibacterial and disinfected while realizing high-efficiency filtration. There are technical problems.

The technical scheme provided by the present invention is:

A kind of manufacture method of antibacterial disinfection air filter material, it comprises the following steps:

(S1) water-based polyurethane is put into a solvent and dissolved to obtain a mixed solution;

(S2) adding silver-loaded graphene to the mixed solution to form a spinning solution;

(S3) using the spinning solution to perform electrospinning to form an electrospinning non-woven fabric; the electrospinning non-woven fabric includes water-based polyurethane fibers, and the interior of the water-based polyurethane fibers is mixed with silver-loaded graphene;

(S4) TiO ₂ thin films were prepared by deposition on the surface of electrospun non-woven fabrics.

A further improvement of the present invention is that the solvent used in step (S1) is N,N-dimethylformamide solvent system; the mass concentration of polyurethane in the mixed solution is 5-10%.

A further improvement of the present invention is that step (S1) comprises the following steps:

(S11) successively carry out slice cleaning to the water-based polyurethane;

(S12) water-based polyurethane is placed in the solvent and mechanically stirred; the stirring time is 18-24h;

(S13) Ultrasonic defoaming is performed on the mixed solution; the ultrasonic defoaming time is 3-4h.

A further improvement of the present invention is that after adding the silver-loaded graphene to the mixed solution, mechanical stirring and mixing and ultrasonic defoaming treatment are performed in sequence; the time for mechanical stirring and mixing is 3-4 hours; and the time for ultrasonic defoaming is 3-4 hours.

A further improvement of the present invention is that, in the spinning solution, the mass ratio of polyurethane to silver-loaded graphene is 1-5 wt%.

A further improvement of the present invention is that, in step (S3), the electrospinning voltage in the electrospinning process is 20-30kV, the solution advancing rate is 0.003-0.008mm/s, the spinning distance is 18±3cm, the receiver The rotating speed is 35-40r/min.

A further improvement of the present invention is that, in step (S3), the ambient temperature of the electrospinning is 25-30° C., and the ambient humidity is 35-40%.

A further improvement of the present invention lies in that, in step (S4), the TiO ₂ film is prepared by the process of radio frequency magnetron sputtering; the flow rate of high purity argon gas by radio frequency magnetron sputtering is 10sccm～30sccm, and the local vacuum degree is 5×10 ^-4 Pa～1×10 ^-3 Pa; the sputtering power of radio frequency magnetron sputtering is 200W～300W.

Compared with the prior art, the present invention has the following beneficial effects: the TiO ₂ film can degrade various microorganisms, including viruses, spores, bacteria and protozoa. In addition, in the electrospinning non-woven fabric, after absorbing water vapor in the air (moisture in the air or moisture generated by breathing), the surface of the water-based polyurethane fiber becomes soft and becomes a gel-like substance. Polyurethane fibers can better adhere to the particles in the air, and also make the silver-loaded graphene in the water-based polyurethane fibers easier to contact with microorganisms in the air, and play a role in antibacterial disinfection. The existence of water molecules makes a small amount of silver become silver ions, which can inactivate the microorganisms it comes into contact with, further enhancing the effect of disinfection and antibacterial.

Description of drawings

Other features, objects and advantages of the present invention will become more apparent by reading the detailed description of non-limiting embodiments with reference to the following drawings:

FIG. 1 is a schematic structural diagram of an antibacterial and disinfecting air filter material.

Detailed ways

The present invention will be described in detail below with reference to specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that, for those skilled in the art, several changes and improvements can be made without departing from the inventive concept. These all belong to the protection scope of the present invention.

Example 1:

The present embodiment provides a method for manufacturing an antibacterial and disinfecting air filter material, which comprises the following steps:

(S1) The aqueous polyurethane is put into a solvent and dissolved to obtain a mixed solution.

In this step, the solvent used is N,N-dimethylformamide solvent system; the mass concentration of polyurethane in the mixed solution is 5%. Specifically, in the process of configuring the mixed solution, the water-based polyurethane is sequentially cleaned for slices; then the water-based polyurethane is placed in a solvent and mechanically stirred; the stirring time is 24 hours; after the stirring is completed, the mixed solution is subjected to ultrasonic defoaming treatment; ultrasonic The defoaming time was 3h.

(S2) adding silver-loaded graphene to the mixed solution to form a spinning solution.

In this step, after adding silver-loaded graphene to the mixed solution, mechanical stirring and mixing and ultrasonic defoaming treatment are performed in sequence; the time for mechanical stirring and mixing is 3-4 hours; the time for ultrasonic defoaming is 3-4 hours. In the final spinning solution, the mass ratio of polyurethane to silver-loaded graphene is 3wt%.

(S3) Electrospinning is performed by using the spinning solution to form an electrospinning non-woven fabric. The electrospinning non-woven fabric includes water-based polyurethane fibers, and the interior of the water-based polyurethane fibers is mixed with silver-loaded graphene;

In this step, the electrospinning voltage was 25kV, the solution advancing rate was 0.005mm/s, the spinning distance was 20cm, and the receiver rotational speed was 35r/min. The ambient temperature for electrospinning was 28°C and the ambient humidity was 35%.

(S4) TiO ₂ thin films were prepared by deposition on the surface of electrospun non-woven fabrics.

In this step, the TiO ₂ thin film is prepared by the process of radio frequency magnetron sputtering. The equipment used for RF magnetron sputtering is a magnetron sputtering coating system (MSP-300C type). The steps of preparing the TiO ₂ thin film specifically include: placing the electrospinning non-woven fabric as a base material on the sample stage, installing the TiO ₂ target in the magnetron radio frequency sputtering target, and placing the magnetron sputtering coating system The sputtering chamber is evacuated until the vacuum degree in the chamber reaches 9×10 ^-4 Pa; then high-purity argon gas is introduced into the sputtering chamber until the pressure in the sputtering chamber reaches 0.7Pa, and the flow rate of high-purity argon gas is 10sccm. The RF power applied on the _TiO2 target was turned on, and the sputtering of the _TiO2 target was started to clean the surface of the _TiO2 target, and the sputtering time was 1 min. After the surface of the TiO ₂ target was cleaned, the radio frequency power applied to the TiO ₂ target was turned off, and the radio frequency sputtering power was set to 250W. Rotate the substrate to be sputtered to the TiO ₂ target position, turn on the radio frequency power supply of the TiO ₂ target position, and sputter at 80° C. for 15 min to obtain a TiO ₂ thin film.

After the step (S4), the antibacterial and disinfecting air filter material of the present embodiment is finally obtained. Its structure is shown in Figure 1, which includes an electrospinning non-woven fabric 1 and a _TiO2 film 2 attached to its surface. TiO ₂ film 2 can degrade a variety of microorganisms, including viruses, spores, bacteria and protozoa. In addition, in the electrospinning non-woven fabric 1, after absorbing water vapor in the air (moisture in the air or moisture generated by breathing), the surface of the water-based polyurethane fiber becomes soft and becomes a gel-like substance. The water-based polyurethane fiber can better adhere to the particles in the air, and it can also make the silver-loaded graphene in the water-based polyurethane fiber easier to contact with microorganisms in the air, and play the role of antibacterial and disinfection. The existence of water molecules makes a small amount of silver become silver ions, which can inactivate the microorganisms it comes into contact with, further enhancing the effect of disinfection and antibacterial.

Example 2:

The present embodiment provides a method for manufacturing an antibacterial and disinfecting air filter material, which comprises the following steps:

(S1) The aqueous polyurethane is put into a solvent and dissolved to obtain a mixed solution.

In this step, the solvent used is N,N-dimethylformamide solvent system; the mass concentration of polyurethane in the mixed solution is 7%. Specifically, in the process of configuring the mixed solution, the water-based polyurethane is sequentially cleaned for slices; then the water-based polyurethane is placed in a solvent and mechanically stirred; the stirring time is 24 hours; after the stirring is completed, the mixed solution is subjected to ultrasonic defoaming treatment; ultrasonic The defoaming time was 3h.

(S2) adding silver-loaded graphene to the mixed solution to form a spinning solution.

In this step, after adding silver-loaded graphene to the mixed solution, mechanical stirring and mixing and ultrasonic defoaming treatment are performed in sequence; the time for mechanical stirring and mixing is 3-4 hours; the time for ultrasonic defoaming is 3-4 hours. In the final spinning solution, the mass ratio of polyurethane to silver-loaded graphene is 3wt%.

(S3) Electrospinning is performed by using the spinning solution to form an electrospinning non-woven fabric. The electrospinning non-woven fabric includes water-based polyurethane fibers, and the interior of the water-based polyurethane fibers is mixed with silver-loaded graphene;

In this step, the electrospinning voltage was 25kV, the solution advancing rate was 0.007mm/s, the spinning distance was 20cm, and the receiver rotational speed was 40r/min. The ambient temperature for electrospinning was 28°C and the ambient humidity was 35%. The ratio of the spinning solution and the process parameters of electrospinning in this embodiment make the thickness and length of the water-based polyurethane fibers in an appropriate range, and the adhesion between the water-based polyurethane fibers is less, which makes the electrospinning non-woven fabric in While ensuring the filtering effect, it has a small filtering resistance.

(S4) TiO ₂ thin films were prepared by deposition on the surface of electrospun non-woven fabrics.

In this step, the TiO ₂ thin film is prepared by the process of radio frequency magnetron sputtering. The equipment used for RF magnetron sputtering is a magnetron sputtering coating system (MSP-300C type). The steps of preparing the TiO ₂ film specifically include: placing the electrospinning non-woven fabric as a base material on the sample stage, installing the TiO ₂ target in the magnetron radio frequency sputtering target, and placing the magnetron sputtering coating system The sputtering chamber is evacuated until the vacuum degree in the chamber reaches 9×10 ^-4 Pa; then high-purity argon gas is introduced into the sputtering chamber until the pressure in the sputtering chamber reaches 0.7Pa, and the flow rate of high-purity argon gas is 10sccm. The RF power applied on the _TiO2 target was turned on, and the sputtering of the _TiO2 target was started to clean the surface of the _TiO2 target, and the sputtering time was 1 min. After the surface of the TiO ₂ target was cleaned, the radio frequency power applied to the TiO ₂ target was turned off, and the radio frequency sputtering power was set to 250W. Rotate the substrate to be sputtered to the TiO ₂ target position, turn on the radio frequency power supply of the TiO ₂ target position, and sputter at 80° C. for 15 min to obtain a TiO ₂ thin film.

After the step (S4), the antibacterial and disinfecting air filter material of the present embodiment is finally obtained. Its structure is shown in Figure 1, which includes an electrospinning non-woven fabric 1 and a _TiO2 film 2 attached to its surface.

Example 3:

The present embodiment provides a method for manufacturing an antibacterial and disinfecting air filter material, which comprises the following steps:

(S1) The aqueous polyurethane is put into a solvent and dissolved to obtain a mixed solution.

In this step, the solvent used is N,N-dimethylformamide solvent system; the mass concentration of polyurethane in the mixed solution is 10%. Specifically, in the process of configuring the mixed solution, the water-based polyurethane is sequentially cleaned for slices; then the water-based polyurethane is placed in a solvent and mechanically stirred; the stirring time is 24 hours; after the stirring is completed, the mixed solution is subjected to ultrasonic defoaming treatment; ultrasonic The defoaming time was 3h.

(S2) adding silver-loaded graphene to the mixed solution to form a spinning solution.

In this step, after adding silver-loaded graphene to the mixed solution, mechanical stirring and mixing and ultrasonic defoaming treatment are performed in sequence; the time for mechanical stirring and mixing is 3-4 hours; the time for ultrasonic defoaming is 3-4 hours. In the final spinning solution, the mass ratio of polyurethane to silver-loaded graphene is 3wt%.

(S3) Electrospinning is performed by using the spinning solution to form an electrospinning non-woven fabric. The electrospinning non-woven fabric includes water-based polyurethane fibers, and the interior of the water-based polyurethane fibers is mixed with silver-loaded graphene;

In this step, the electrospinning voltage is 30kV, the solution advancing rate is 0.008mm/s, the spinning distance is 20cm, and the receiver rotational speed is 35-40r/min. The ambient temperature for electrospinning was 28°C and the ambient humidity was 35%. The ratio of the spinning solution and the process parameters of electrospinning in this embodiment make the thickness and length of the water-based polyurethane fibers in an appropriate range, and the adhesion between the water-based polyurethane fibers is less, which makes the electrospinning non-woven fabric in While ensuring the filtering effect, it has a small filtering resistance.

(S4) TiO ₂ thin films were prepared by deposition on the surface of electrospun non-woven fabrics.

In this step, the TiO ₂ thin film is prepared by the process of radio frequency magnetron sputtering. The equipment used for RF magnetron sputtering is a magnetron sputtering coating system (MSP-300C type). The steps of preparing the TiO ₂ thin film specifically include: placing the electrospinning non-woven fabric as a base material on the sample stage, installing the TiO ₂ target in the magnetron radio frequency sputtering target, and placing the magnetron sputtering coating system The sputtering chamber is evacuated until the vacuum degree in the chamber reaches 9×10 ^-4 Pa; then high-purity argon gas is introduced into the sputtering chamber until the pressure in the sputtering chamber reaches 0.7Pa, and the flow rate of high-purity argon gas is 10sccm. The RF power applied on the _TiO2 target was turned on, and the sputtering of the _TiO2 target was started to clean the surface of the _TiO2 target, and the sputtering time was 1 min. After the surface of the TiO ₂ target was cleaned, the radio frequency power applied to the TiO ₂ target was turned off, and the radio frequency sputtering power was set to 250W. Rotate the substrate to be sputtered to the TiO ₂ target position, turn on the radio frequency power supply of the TiO ₂ target position, and sputter at 80° C. for 15 min to obtain a TiO ₂ thin film.

After the step (S4), the antibacterial and disinfecting air filter material of the present embodiment is finally obtained. Its structure is shown in Figure 1, which includes an electrospinning non-woven fabric 1 and a _TiO2 film 2 attached to its surface.

Comparative Example 1:

This comparative example provides a kind of manufacture method of antibacterial disinfection air filter material, it comprises the following steps:

(S1) The aqueous polyurethane is put into a solvent and dissolved to obtain a mixed solution.

In this step, the solvent used is N,N-dimethylformamide solvent system; the mass concentration of polyurethane in the mixed solution is 4%. Specifically, in the process of configuring the mixed solution, the water-based polyurethane is sequentially cleaned for slices; then the water-based polyurethane is placed in a solvent and mechanically stirred; the stirring time is 24 hours; after the stirring is completed, the mixed solution is subjected to ultrasonic defoaming treatment; ultrasonic The defoaming time was 3h.

(S2) adding silver-loaded graphene to the mixed solution to form a spinning solution.

In this step, after adding silver-loaded graphene to the mixed solution, mechanical stirring and mixing and ultrasonic defoaming treatment are performed in sequence; the time for mechanical stirring and mixing is 3-4 hours; the time for ultrasonic defoaming is 3-4 hours. In the final spinning solution, the mass ratio of polyurethane to silver-loaded graphene is 3wt%.

(S3) Electrospinning is performed by using the spinning solution to form an electrospinning non-woven fabric. The electrospinning non-woven fabric includes water-based polyurethane fibers, and the interior of the water-based polyurethane fibers is mixed with silver-loaded graphene;

In this step, the electrospinning voltage was 20kV, the solution advancing rate was 0.003mm/s, the spinning distance was 20cm, and the receiver rotational speed was 35r/min. The ambient temperature for electrospinning was 28°C and the ambient humidity was 40%.

(S4) TiO ₂ thin films were prepared by deposition on the surface of electrospun non-woven fabrics.

In this step, the TiO ₂ thin film is prepared by the process of radio frequency magnetron sputtering. The equipment used for RF magnetron sputtering is a magnetron sputtering coating system (MSP-300C type). The steps of preparing the TiO ₂ film specifically include: placing the electrospinning non-woven fabric as a base material on the sample stage, installing the TiO ₂ target in the magnetron radio frequency sputtering target, and placing the magnetron sputtering coating system The sputtering chamber is evacuated until the vacuum degree in the chamber reaches 9×10 ^-4 Pa; then high-purity argon gas is introduced into the sputtering chamber until the pressure in the sputtering chamber reaches 0.7Pa, and the flow rate of high-purity argon gas is 10sccm. The RF power applied on the _TiO2 target was turned on, and the sputtering of the _TiO2 target was started to clean the surface of the _TiO2 target, and the sputtering time was 1 min. After the surface of the TiO ₂ target was cleaned, the radio frequency power applied to the TiO ₂ target was turned off, and the radio frequency sputtering power was set to 250W. Rotate the substrate to be sputtered to the TiO ₂ target position, turn on the radio frequency power supply of the TiO ₂ target position, and sputter at 80° C. for 15 min to obtain a TiO ₂ thin film.

After step (S4), the antibacterial and disinfecting air filter material of this comparative example is finally obtained. Its structure is shown in Figure 1, which includes an electrospinning non-woven fabric 1 and a _TiO2 film 2 attached to its surface.

Comparative Example 2:

This comparative example provides a kind of manufacture method of antibacterial disinfection air filter material, it comprises the following steps:

(S1) The aqueous polyurethane is put into a solvent and dissolved to obtain a mixed solution.

In this step, the solvent used is N,N-dimethylformamide solvent system; the mass concentration of polyurethane in the mixed solution is 12%. Specifically, in the process of configuring the mixed solution, the water-based polyurethane is sequentially cleaned for slices; then the water-based polyurethane is placed in a solvent and mechanically stirred; the stirring time is 24 hours; after the stirring is completed, the mixed solution is subjected to ultrasonic defoaming treatment; ultrasonic The defoaming time was 3h.

(S2) adding silver-loaded graphene to the mixed solution to form a spinning solution.

In this step, after adding silver-loaded graphene to the mixed solution, mechanical stirring and mixing and ultrasonic defoaming treatment are performed in sequence; the time for mechanical stirring and mixing is 3-4 hours; the time for ultrasonic defoaming is 3-4 hours. In the final spinning solution, the mass ratio of polyurethane to silver-loaded graphene is 3wt%.

(S3) Electrospinning is performed by using the spinning solution to form an electrospinning non-woven fabric. The electrospinning non-woven fabric includes water-based polyurethane fibers, and the interior of the water-based polyurethane fibers is mixed with silver-loaded graphene;

In this step, the electrospinning voltage was 30kV, the solution advancing rate was 0.008mm/s, the spinning distance was 20cm, and the receiver rotational speed was 35r/min. The ambient temperature for electrospinning was 28°C and the ambient humidity was 35%.

(S4) TiO ₂ thin films were prepared by deposition on the surface of electrospun non-woven fabrics.

In this step, the TiO ₂ thin film is prepared by the process of radio frequency magnetron sputtering. The equipment used for RF magnetron sputtering is a magnetron sputtering coating system (MSP-300C type). The steps of preparing the TiO ₂ film specifically include: placing the electrospinning non-woven fabric as a base material on the sample stage, installing the TiO ₂ target in the magnetron radio frequency sputtering target, and placing the magnetron sputtering coating system The sputtering chamber is evacuated until the vacuum degree in the chamber reaches 9×10 ^-4 Pa; then high-purity argon gas is introduced into the sputtering chamber until the pressure in the sputtering chamber reaches 0.7Pa, and the flow rate of high-purity argon gas is 10sccm. The RF power applied on the _TiO2 target was turned on, and the sputtering of the _TiO2 target was started to clean the surface of the _TiO2 target, and the sputtering time was 1 min. After the surface of the TiO ₂ target was cleaned, the radio frequency power applied to the TiO ₂ target was turned off, and the radio frequency sputtering power was set to 250W. Rotate the substrate to be sputtered to the TiO ₂ target position, turn on the radio frequency power supply of the TiO ₂ target position, and sputter at 80° C. for 15 min to obtain a TiO ₂ thin film.

After step (S4), the antibacterial and disinfecting air filter material of this comparative example is finally obtained. Its structure is shown in Figure 1, which includes an electrospinning non-woven fabric 1 and a _TiO2 film 2 attached to its surface.

Comparative Example 3:

This comparative example provides a kind of manufacture method of antibacterial disinfection air filter material, it comprises the following steps:

(S1) The aqueous polyurethane is put into a solvent and dissolved to obtain a mixed solution.

In this step, the solvent used is N,N-dimethylformamide solvent system; the mass concentration of polyurethane in the mixed solution is 14%. Specifically, in the process of configuring the mixed solution, the water-based polyurethane is sequentially cleaned for slices; then the water-based polyurethane is placed in a solvent and mechanically stirred; the stirring time is 24 hours; after the stirring is completed, the mixed solution is subjected to ultrasonic defoaming treatment; ultrasonic The defoaming time was 3h.

(S2) adding silver-loaded graphene to the mixed solution to form a spinning solution.

In this step, after adding silver-loaded graphene to the mixed solution, mechanical stirring and mixing and ultrasonic defoaming treatment are performed in sequence; the time for mechanical stirring and mixing is 3-4 hours; the time for ultrasonic defoaming is 3-4 hours. In the final spinning solution, the mass ratio of polyurethane to silver-loaded graphene is 3wt%.

(S3) Electrospinning is performed by using the spinning solution to form an electrospinning non-woven fabric. The electrospinning non-woven fabric includes water-based polyurethane fibers, and the interior of the water-based polyurethane fibers is mixed with silver-loaded graphene;

In this step, the electrospinning voltage was 30kV, the solution advancing rate was 0.008mm/s, the spinning distance was 20cm, and the receiver rotational speed was 35r/min. The ambient temperature for electrospinning was 28°C and the ambient humidity was 35%.

(S4) TiO ₂ thin films were prepared by deposition on the surface of electrospun non-woven fabrics.

In this step, the TiO ₂ thin film is prepared by the process of radio frequency magnetron sputtering. The equipment used for RF magnetron sputtering is a magnetron sputtering coating system (MSP-300C type). The steps of preparing the TiO ₂ film specifically include: placing the electrospinning non-woven fabric as a base material on the sample stage, installing the TiO ₂ target in the magnetron radio frequency sputtering target, and placing the magnetron sputtering coating system The sputtering chamber is evacuated until the vacuum degree in the chamber reaches 9×10 ^-4 Pa; then high-purity argon gas is introduced into the sputtering chamber until the pressure in the sputtering chamber reaches 0.7Pa, and the flow rate of high-purity argon gas is 10sccm. The RF power applied on the _TiO2 target was turned on, and the sputtering of the _TiO2 target was started to clean the surface of the _TiO2 target, and the sputtering time was 1 min. After the surface of the TiO ₂ target was cleaned, the radio frequency power applied to the TiO ₂ target was turned off, and the radio frequency sputtering power was set to 250W. Rotate the substrate to be sputtered to the TiO ₂ target position, turn on the radio frequency power supply of the TiO ₂ target position, and sputter at 80° C. for 15 min to obtain a TiO ₂ thin film.

After step (S4), the antibacterial and disinfecting air filter material of this comparative example is finally obtained. Its structure is shown in Figure 1, which includes an electrospinning non-woven fabric 1 and a _TiO2 film 2 attached to its surface.

Comparative Example 4:

This comparative example provides a kind of manufacture method of antibacterial disinfection air filter material, it comprises the following steps:

(S1) The aqueous polyurethane is put into a solvent and dissolved to obtain a mixed solution.

In this step, the solvent used is N,N-dimethylformamide solvent system; the mass concentration of polyurethane in the mixed solution is 5%. Specifically, in the process of configuring the mixed solution, the water-based polyurethane is sequentially cleaned for slices; then the water-based polyurethane is placed in a solvent and mechanically stirred; the stirring time is 24 hours; after the stirring is completed, the mixed solution is subjected to ultrasonic defoaming treatment; ultrasonic The defoaming time was 3h.

(S2) Electrospinning is performed by using the mixed solution to form an electrospinning non-woven fabric. The electrospinning non-woven fabric includes water-based polyurethane fibers, and the interior of the water-based polyurethane fibers is mixed with silver-loaded graphene;

In this step, the electrospinning voltage was 25kV, the solution advancing rate was 0.005mm/s, the spinning distance was 20cm, and the receiver rotational speed was 35r/min. The ambient temperature for electrospinning was 28°C and the ambient humidity was 35%. The ratio of the spinning solution and the process parameters of electrospinning in this embodiment make the thickness and length of the water-based polyurethane fibers in an appropriate range, and the adhesion between the water-based polyurethane fibers is less, which makes the electrospinning non-woven fabric in While ensuring the filtering effect, it has a small filtering resistance.

(S3) TiO ₂ thin films were prepared by deposition on the surface of electrospun nonwoven fabrics.

In this step, the TiO ₂ thin film is prepared by the process of radio frequency magnetron sputtering. The equipment used for RF magnetron sputtering is a magnetron sputtering coating system (MSP-300C type). The steps of preparing the TiO ₂ thin film specifically include: placing the electrospinning non-woven fabric as a base material on the sample stage, installing the TiO ₂ target in the magnetron radio frequency sputtering target, and placing the magnetron sputtering coating system The sputtering chamber is evacuated until the vacuum degree in the chamber reaches 9×10 ^-4 Pa; then high-purity argon gas is introduced into the sputtering chamber until the pressure in the sputtering chamber reaches 0.7Pa, and the flow rate of high-purity argon gas is 10sccm. The RF power applied on the _TiO2 target was turned on, and the sputtering of the _TiO2 target was started to clean the surface of the _TiO2 target, and the sputtering time was 1 min. After the surface of the TiO ₂ target was cleaned, the radio frequency power applied to the TiO ₂ target was turned off, and the radio frequency sputtering power was set to 250W. Rotate the substrate to be sputtered to the TiO ₂ target position, turn on the radio frequency power supply of the TiO ₂ target position, and sputter at 80° C. for 15 min to obtain a TiO ₂ thin film.

After step (S3), the antibacterial and disinfecting air filter material of this comparative example is finally obtained.

Test 1:

In this test, the difference between the antibacterial effects of Comparative Example 4 and Example 1 was examined. The samples of Example 1 and Comparative Example 4 were added to the broth containing the same concentration of Staphylococcus aureus by the micro-broth dilution method, and cultured, and the final concentration of the flora was shown in Table-1:

Table-1 Comparison of antibacterial effects

As can be seen from Table 1, the difference between Example 1 and Comparative Example 4 is only that silver-loaded graphene is mixed in Example 1. Therefore, it can be seen from this test that after adding silver-loaded graphene, there can be antibacterial disinfection.

Example 2:

In this test, the filtration efficiency and filtration resistance of Examples 1 to 3 and Comparative Examples 1 to 4 were respectively tested. The test results are shown in Table-2 and Table-3:

Table-2 Comparison of Filtration Efficiency

Table-3 Filter resistance comparison

Combining Table 2 and Table 3, it can be seen that under the same conditions, Example 2 has the highest filtration efficiency and the lowest filtration resistance. It is the best embodiment. Both Example 1 and Example 3 achieve 100% pm2.5 (or the unfiltered particles are lower than the detection limit of the test equipment), and the filtration resistance is also within the standard of YY0469-2004 technical requirements for medical surgical masks. However, in Comparative Examples 1 to 3, the filtration efficiency and/or filtration resistance are not ideal. The reason is that the concentration of the spinning solution in Comparative Example 1 is low, and the solvent is too late to volatilize completely. At the same time, due to the viscoelasticity of the polymer molecular chain and the polyurethane It is an elastomer itself, so the molecular chain tends to shrink, making it easier for spinning fibers to form beads. Comparative Examples 2 and 3 are water-based polyurethane products. Because the concentration is higher than a certain critical value, the entanglement between fibers increases, and the solution When the jet is stretched by the electric field, the volatilization of the solution is incomplete and it is easy to stick together.

It can be seen from the data of test 2 and the parameters of each example and the comparative example that the ratio of spinning solution plays a decisive role in the filtration effect and over-resistance of the final product. Both of them reach optimal values around the parameters of Example 2.

The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above-mentioned specific embodiments, and those skilled in the art can make various changes or modifications within the scope of the claims, which do not affect the essential content of the present invention. The embodiments of the present application and features in the embodiments may be arbitrarily combined with each other without conflict.

Claims (8)

1. A manufacturing method of an antibacterial and disinfectant air filter material is characterized by comprising the following steps:

(S1) dissolving the waterborne polyurethane in a solvent to obtain a mixed solution;

(S2) adding silver-loaded graphene into the mixed solution to form a spinning solution;

(S3) performing electrospinning using the spinning solution to form an electrospun non-woven fabric; the electrostatic spinning non-woven fabric comprises aqueous polyurethane fibers, wherein silver-loaded graphene is mixed in the aqueous polyurethane fibers;

(S4) preparing TiO on the surface of the electrostatic spinning non-woven fabric by deposition₂A film.

2. The method of claim 1, wherein the solvent used in the step (S1) is N, N-dimethylformamide solvent system; the mass concentration of polyurethane in the mixed solution is 5-10%.

3. The manufacturing method of an antibacterial sterilizing air filtering material according to claim 1 or 2, characterized in that the step (S1) comprises the steps of:

(S11) sequentially carrying out slice cleaning on the waterborne polyurethane;

(S12) placing the aqueous polyurethane in the solvent and mechanically stirring; stirring for 18-24 h;

(S13) carrying out ultrasonic defoaming treatment on the mixed solution; the time for ultrasonic defoaming is 3-4 h.

4. The method for manufacturing an antibacterial and disinfectant air filter material according to claim 1, wherein after the silver-loaded graphene is added to the mixed solution, the mechanical stirring and mixing and the ultrasonic defoaming treatment are sequentially performed; the time for mechanical stirring and mixing is 3-4 h; the time for ultrasonic defoaming is 3-4 h.

5. The method for manufacturing an antibacterial and disinfectant air filter material according to claim 1, wherein the mass ratio of polyurethane to silver-loaded graphene in the spinning solution is 1-5 wt%.

6. The method of claim 1, wherein in the step (S3), the voltage of the electrostatic spinning in the electrostatic spinning process is 20-30kV, the solution advancing speed is 0.003-0.008mm/S, the spinning distance is 18 ± 3cm, and the receiver rotation speed is 35-40 r/min.

7. The method of claim 6, wherein in the step (S3), the ambient temperature of the electrostatic spinning is 25-30 ℃ and the ambient humidity is 35-40%.

8. The method for manufacturing an antibacterial and antiseptic air filtering material as claimed in claim 1, wherein in the step (S4), the TiO is prepared by a radio frequency magnetron sputtering process₂A film; the flow rate of the radio frequency magnetron sputtering high-purity argon is 10sccm to 30sccm, and the local vacuum degree is 5 multiplied by 10^-4Pa～1×10^-3Pa; the sputtering power of the radio frequency magnetron sputtering is 200W-300W.

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