Disinfecting non-woven fabric, preparation method and application thereof

Abstract

The application discloses a disinfection and sterilization non-woven fabric, a preparation method and application. The disinfection and sterilization non-woven fabric comprises disinfection and sterilization functional materials, adopts resin slices and disinfection and sterilization functional resin master batches to be mixed and melted, and is prepared through spinning and web laying. The resin slice material is selected from PP propylene and / or PET polyester. The disinfection and sterilization functional resin master batch comprises disinfection and sterilization functional materials, the disinfection and sterilization functional materials are porous inorganic titanium zirconium phosphate functional materials, and the mass content of the disinfection and sterilization functional materials in the disinfection and sterilization non-woven fabric is 1-30%. The disinfection and sterilization non-woven fabric is uniform in distribution of disinfection and sterilization functional materials on the surface of non-woven fabric fibers and is easy to produce. The disinfection and sterilization non-woven fabric can be used for producing masks, protective clothes, medical bag cloth, surgical pad cloth and the like.

Description

Technical Field

[0001] This invention relates to a sterilizing and disinfecting nonwoven fabric, its preparation method, and its application, belonging to the field of special nonwoven fabric production technology. Background Technology

[0002] Bacteria and viruses that can cause infection in humans or other organisms are collectively called pathogens. Bacteria are single-celled organisms with complete cell walls, cell membranes, cytoplasm, and nucleoplasm, while viruses have a simple structure, lacking cellular structure and mainly composed of nucleic acids (DNA or RNA) and an outer protein coat. They cannot survive independently and must parasitize living cells. The spread and infection of bacteria and viruses have always been one of the greatest threats to humankind. Historically, serious plagues caused by bacterial infections include plague (Black Death) caused by Yersinia pestis, cholera caused by Vibrio cholerae, tuberculosis caused by Mycobacterium tuberculosis, and anthrax caused by Bacillus anthracis. Diseases with high mortality rates caused by viral infections include AIDS caused by HIV and Ebola virus disease caused by Ebola virus. In recent decades, viral infectious diseases have shown a continuous upward trend, seriously endangering people's health and safety.

[0003] Besides developing vaccines to boost immunity, personal protective equipment is one of the most effective ways to block the spread of infectious diseases caused by bacteria and viruses. Traditionally, all protective equipment against bacteria and viruses, such as masks and protective clothing, only isolates them; they do not effectively kill them. In particular, the use of modern central air conditioning systems can actually facilitate transmission if bacteria and viruses are not eliminated within the ventilation system. Therefore, there is an urgent need to develop materials and protective products with antibacterial and antiviral properties, such as masks, protective clothing, and air conditioning filters, for personal, family, and large public places like hospitals and train stations. These products should effectively kill bacteria and viruses while isolating them, thereby effectively curbing their spread and infection, and protecting public health.

[0004] Both bacteria and viruses are microorganisms. Current disinfection methods rely on physical and chemical means to denature and inactivate them, thus eliminating their infectivity. However, the disinfectants used in these methods cannot be applied to masks, protective clothing, or air conditioning systems. Therefore, there is a need to develop functional materials that can be immobilized and are effective at room temperature. Chinese patent CN1242815C discloses a type of porous solid material with adsorption and inactivation effects on viruses. Testing showed it to have a direct inactivation effect on parainfluenza virus and an inhibitory effect on human herpesvirus and human adenovirus, but it has not been applied to protective products. Chinese patent CN 112871129A discloses a method for preparing and applying a macroporous functional material for adsorbing and inactivating viruses. By loading the adsorbing and inactivating virus functional material onto a macroporous carrier, it successfully solves the problem of effective virus adsorption by the material. Chinese patent CN 112878037A discloses a polypropylene meltblown fabric for adsorbing and inactivating viruses, its production method, and its application. This involves spraying a nanomaterial for adsorbing and inactivating viruses onto semi-finished polypropylene meltblown fabric fibers within a specific temperature range. Chinese patent CN 112878038A discloses a nonwoven fabric for adsorbing and inactivating viruses, its production method, and its application. The method involves immobilizing adsorbent and inactivating virus nanomaterials onto the nonwoven fabric using a dispersant and adhesive. This nonwoven fabric or meltblown fabric exhibits direct adsorption and inactivation of the novel coronavirus SARS-CoV-2 and can be used to produce masks, protective clothing, air purifiers, and air conditioning filters with virus adsorption and inactivation functions. However, the spraying or immobilization techniques employed in this method are complex, and the distribution of the adsorbent and inactivating virus nanomaterials on the surface of the meltblown fabric or nonwoven fabric fibers is uneven. Summary of the Invention

[0005] According to one aspect of the present invention, a sterilizing and disinfecting nonwoven fabric is provided, characterized in that the sterilizing and disinfecting nonwoven fabric comprises a sterilizing and disinfecting functional material, which is prepared by mixing and melting resin chips and sterilizing and disinfecting functional resin masterbatch, and then spinning and web laying.

[0006] The resin chip material is selected from PP polypropylene and / or PET polyester;

[0007] The sterilization and disinfection functional resin masterbatch contains sterilization and disinfection functional materials;

[0008] The sterilization and disinfection functional material is a porous inorganic titanium zirconium phosphate functional material.

[0009] The mass content of the sterilizing and disinfecting functional material in the sterilizing and disinfecting nonwoven fabric is 1-30%.

[0010] Optionally, the mass content of the sterilizing and disinfecting functional material in the sterilizing and disinfecting nonwoven fabric is selected from any value of 1%, 5%, 10%, 15%, 20%, 25%, 30% or a range between any two of the above points.

[0011] Optionally, the chemical formula of the porous inorganic titanium zirconium phosphate functional material is Ti. n Zr (1-n) (HPO4)2 (0 < n < 1) has redox properties.

[0012] Optionally, the interlayer pore size of the porous inorganic titanium zirconium phosphate functional material is 50–200 nm.

[0013] Optionally, the virus is a novel coronavirus (SARS-CoV-2) and / or influenza A virus (H1N1).

[0014] Optionally, the bacteria is at least one of Escherichia coli, Staphylococcus aureus, and Candida albicans.

[0015] According to another aspect of the present invention, a method for preparing the above-described sterilizing and disinfecting nonwoven fabric is provided, characterized in that the preparation method includes the following steps:

[0016] (a) Mix the resin chips and sterilization and disinfection functional resin masterbatch in proportion, heat and melt them and stir evenly, wherein the temperature of PET polyester is 270~280℃ and the temperature of PP polypropylene is 220~240℃.

[0017] (b) The resin slurry obtained in step (a) is fed into a screw extruder for high-temperature melt extrusion. The molten resin is pumped into the spinneret by a spinneret metering pump and then extruded into fine fiber filaments through the spinneret plate.

[0018] (c) The fiber filaments ejected in step (b) are stretched by airflow and laid into a web, and then hot rolled by a rolling mill to obtain a sterilizing and disinfecting nonwoven fabric.

[0019] Optionally, the sterilizing nonwoven fabric can be formed into a web on its own or in combination with meltblown nonwoven fabric, including single-layer sterilizing nonwoven fabric (S), sterilizing nonwoven fabric + sterilizing nonwoven fabric (SS) double-layer nonwoven fabric, and sterilizing nonwoven fabric + meltblown nonwoven fabric + sterilizing nonwoven fabric (SMS), sterilizing nonwoven fabric + meltblown nonwoven fabric + meltblown nonwoven fabric + sterilizing nonwoven fabric (SMMS) composite nonwoven fabric.

[0020] Optionally, the sterilizing and disinfecting functional resin masterbatch contains sterilizing and disinfecting functional materials.

[0021] Optionally, the sterilization and disinfection functional material is a porous inorganic titanium zirconium phosphate functional material.

[0022] Optionally, the melting temperature is 220℃~320℃, and the melting time is 2~6h.

[0023] Optionally, the melting temperature is selected from any value among 220°C, 240°C, 250°C, 280°C, 290°C, 300°C, and 320°C, or a range between any two of the above points.

[0024] Optionally, the melting time is selected from any value among 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, and 6h, or a range between any two of the above points.

[0025] Optionally, the preparation method of the sterilizing and disinfecting functional resin masterbatch includes the following steps:

[0026] (a) The resin chips are heated and melted, wherein the temperature for PP polypropylene is 220-240°C and the temperature for PET polyester is 270-280°C;

[0027] (b) Add porous inorganic titanium zirconium phosphate functional material to the molten resin obtained in (a), stir evenly, and then use a high-speed shear emulsifier to further mix and circulate to obtain resin slurry;

[0028] (c) The resin slurry obtained in step (b) is fed into an extruder and drawn into strips; strip-shaped material is obtained;

[0029] (d) After the strip material extruded in step (c) is cooled with water, it is fed into a pelletizer to obtain sterilized and disinfected resin masterbatch.

[0030] Optionally, the porous inorganic titanium zirconium phosphate functional material has the chemical formula Ti. n Zr (1-n) (HPO4)2 (0 < n < 1), its preparation method includes the following steps:

[0031] (a) Add titanium precursor, zirconium precursor, phosphorus precursor, template agent and mineralizer to deionized water in proportion, stir, and obtain initial gel;

[0032] (b) The initial gel obtained in step (a) is transferred to a crystallization vessel and dynamically crystallized at 120–180°C for 24–240 hours.

[0033] (c) The crystallized product obtained in step (b) is centrifuged, washed with deionized water until neutral, dried at 80-120°C, and calcined in air at 400-600°C to obtain porous inorganic titanium zirconium phosphate functional material.

[0034] Optionally, the zirconium precursor is selected from at least one of zirconium oxychloride, zirconium nitrate, and tetraethyl zirconate.

[0035] Optionally, the phosphorus precursor is selected from phosphoric acid and / or ammonium phosphate.

[0036] Optionally, the titanium precursor is selected from at least one of tetrabutyl titanate, tetraethyl titanate, and titanium chloride.

[0037] Optionally, the template agent is selected from at least one of ethylenediamine, triethylamine, and 1,3-propanediamine.

[0038] Optionally, the mineralizing agent is selected from HF and / or NH4F.

[0039] Optionally, the molar ratio of the titanium precursor: zirconium precursor: phosphorus precursor: template agent: mineralizer: water is 0.1-3.0: 0.1-3.0: 0.5-5: 0.1-3.0: 0.1-1: 100.

[0040] According to another aspect of the present invention, an application is provided for the sterilization and disinfection nonwoven fabric prepared by the above-described preparation method in masks, protective clothing, medical coverings, and surgical pads.

[0041] In this invention, "S" refers to sterilization and disinfection nonwoven fabric, and "M" refers to meltblown nonwoven fabric.

[0042] The beneficial effects that this invention can produce include:

[0043] The sterilizing and disinfecting nonwoven fabric of the present invention has sterilizing and disinfecting functional materials that are evenly distributed on the surface of the nonwoven fabric fibers. The sterilizing and disinfecting functional materials have a direct inactivation effect on the novel coronavirus (SARS-CoV-2), a direct inactivation effect on influenza A virus (H1N1), and a disinfection effect on Escherichia coli, Candida albicans, and Staphylococcus aureus.

[0044] The sterilizing and disinfecting nonwoven fabric of this invention has a uniformly distributed sterilizing and disinfecting functional material on the surface of the nonwoven fabric fibers, which is easy to produce. It can be used to produce masks, protective clothing, medical drapes, surgical pads, etc. Attached Figure Description

[0045] Figure 1 This is a scanning electron microscope image of the sterilizing and disinfecting nonwoven fabric (S) prepared in Example 4 of the present invention.

[0046] Figure 2 This is a scanning electron microscope image of the sterilizing and disinfecting nonwoven fabric (SMS) prepared in Example 5 of the present invention. Detailed Implementation

[0047] The present invention will now be described in detail with reference to the embodiments, but the present invention is not limited to these embodiments.

[0048] Unless otherwise specified, the raw materials used in the embodiments of the present invention were all purchased through commercial channels.

[0049] Example 1: Preparation of porous inorganic titanium zirconium phosphate functional materials

[0050] (a) Weigh out 1.5 mol tetrabutyl titanate, 1.5 mol tetraethyl zirconate, 3.0 mol phosphoric acid, 2.0 ml triethylamine, 0.5 mol NH4F and 50 mol deionized water in a molar ratio of 1.5:1.5:3.0:2.0:0.5:50. Under stirring conditions, add phosphoric acid, tetraethyl zirconate, tetrabutyl titanate, triethylamine and NH4F to the deionized water in sequence and continue stirring to obtain the initial gel.

[0051] (b) The initial gel obtained in step (a) was transferred to a crystallization vessel and dynamically crystallized at 150°C for 72 hours.

[0052] (c) The crystallized product obtained in step (b) is centrifuged, washed with deionized water until neutral, dried at 120°C, and calcined in air at 550°C to obtain porous inorganic titanium zirconium phosphate functional material.

[0053] The interlayer pore size of the prepared porous inorganic titanium zirconium phosphate functional material was observed to be approximately 120 nm using scanning transmission electron microscopy (STEM).

[0054] Example 2: Adsorption and Inactivation Test of SARS-CoV-2 Delta Strain

[0055] The in vitro efficacy test against the novel coronavirus was conducted at the Wuhan National Biosafety Laboratory (BSL-3) of the Wuhan Institute of Virology, Chinese Academy of Sciences.

[0056] 1. Test substance and reference substance

[0057] Test material: The porous inorganic titanium zirconium phosphate functional material prepared in Example 1.

[0058] Reference object: glass microsphere material.

[0059] 2. Cells and Viruses

[0060] Vero E6 cells: African green monkey kidney cells, derived from the American Type Culture Collection (ATCC).

[0061] The virus: The novel coronavirus (SARS-CoV-2) Delta strain (CSTR: 16533.06.IVCAS6.7585) was obtained from the Microbial Culture Collection Center of Wuhan Institute of Virology, Chinese Academy of Sciences.

[0062] 3. Test methods

[0063] Novel coronavirus solution was uniformly added dropwise to the porous inorganic titanium zirconium phosphate functional material, glass microspheres, and a blank control group, and allowed to react at room temperature for 60 minutes. The virus titers after reaction with the porous inorganic titanium zirconium phosphate functional material and glass microspheres were then measured. By comparing the virus titers in the experimental and control groups, the logarithmic value of virus inactivation and the inhibition rate against the novel coronavirus could be calculated. The virus titer was detected using the plaque method. The logarithmic value of virus inactivation (KL) = the logarithmic value of the average virus titer in the control group (No) - the logarithmic value of the average virus titer in the experimental group (Nx).

[0064] 4. Test Results

[0065] The porous inorganic titanium zirconium phosphate functional material showed an inhibition rate of 99.99% against the novel coronavirus (SARS-CoV-2) Delta strain after a contact incubation time of 60 min. Detailed results are shown in Table 1.

[0066] Table 1

[0067]

[0068]

[0069] Example 3: Preparation of sterilization and disinfection functional resin masterbatch

[0070] (1) Weigh 70 kg of PP polypropylene resin and add it to a stirred tank. Heat the temperature inside the tank to about 230°C and stir to melt. Then add 30 kg of the porous inorganic titanium zirconium phosphate functional material prepared in Example 1 to the tank and stir until uniform.

[0071] (2) Pass the material that was mixed evenly in step (1) into a high-speed shear emulsifier for further mixing and return it to the mixing tank, and run it continuously for 30 minutes to fully mix the molten polypropylene and porous inorganic titanium zirconium phosphate functional material.

[0072] (3) The mixture obtained in step (2) is fed into a twin-screw extruder for melt extrusion granulation. The twin-screw extruder is set with 10 temperature zones, and the set temperatures are 240℃-250℃-260℃-260℃-230℃-230℃-230℃-230℃-250℃. The screw speed of the twin-screw extruder is about 350 r / min. The extruded strip material is cooled in a 30℃ water cooling tank, then dried with hot air, and then cut by a granulator to obtain sterilization and disinfection functional resin masterbatch.

[0073] Example 4: Preparation of sterilizing and disinfecting nonwoven fabric (S)

[0074] (1) Weigh 50 kg of PP polypropylene resin and add it to a mixing tank. Heat the temperature inside the tank to about 230°C and stir to melt. Then add 50 kg of the sterilizing and disinfecting resin masterbatch prepared in Example 3 to the tank and stir until uniform.

[0075] (2) The material mixed evenly in step (1) is fed into a screw extruder for high-temperature melt extrusion. Molten resin is pumped into the spinneret by a spinneret metering pump and then extruded into fine fiber filaments through the spinneret plate.

[0076] (3) The fiber filaments sprayed in step (2) are stretched by airflow and laid into a web, and then hot rolled by a rolling mill to obtain sterilized nonwoven fabric (S).

[0077] Figure 1 Scanning electron microscope image of the sterilizing and disinfecting nonwoven fabric (S) prepared for this invention.

[0078] Example 5: Preparation of sterilizing and disinfecting nonwoven fabric (SMS)

[0079] (1) Weigh 50 kg of PP polypropylene resin and add it to a mixing tank. Heat the temperature inside the tank to about 230°C and stir to melt. Then add 50 kg of the sterilizing and disinfecting resin masterbatch prepared in Example 3 to the tank and stir evenly.

[0080] The uniformly mixed material is fed into a screw extruder for high-temperature melt extrusion. Molten resin is pumped into the spinneret by a spinneret metering pump, and fine fibers are extruded through the spinneret plate. After being stretched by airflow, the fibers are laid into a web to obtain the precursor of sterilized and disinfected nonwoven fabric.

[0081] (2) Weigh 100 kg of PP polypropylene resin and add it to the mixing tank. Heat the temperature inside the tank to about 230°C and stir to melt. The molten material is then transported to a screw extruder for high-temperature melt extrusion. As the fluid flows out of the spinneret, it is impacted by heated high-velocity air and falls onto the sterilized nonwoven fabric precursor prepared in step (1), thus obtaining sterilized nonwoven fabric + meltblown nonwoven fabric precursor.

[0082] (3) Weigh 50 kg of PP polypropylene resin and add it to the mixing tank. Heat the temperature inside the tank to about 230°C and stir to melt. Then add 50 kg of the sterilization and disinfection functional resin masterbatch prepared in Example 3 to the tank and stir evenly.

[0083] The uniformly mixed material is fed into a screw extruder for high-temperature melting and extrusion. Molten resin is pumped into the spinneret by a spinneret metering pump, and fine fibers are sprayed out through the spinneret plate. After being stretched by airflow, the fibers are laid onto the sterilized nonwoven fabric + meltblown nonwoven fabric precursor obtained in step (2) to obtain sterilized nonwoven fabric + meltblown nonwoven fabric + sterilized nonwoven fabric precursor.

[0084] (4) The sterilizing nonwoven fabric, meltblown nonwoven fabric and sterilizing nonwoven fabric precursor obtained in step (3) are hot rolled by a rolling mill to obtain sterilizing nonwoven fabric (SMS).

[0085] Figure 2 Scanning electron microscope image of the sterilizing and disinfecting nonwoven fabric (SMS) prepared according to the present invention.

[0086] Example 6: Test on the adsorption and inactivation of influenza A virus (H1N1) by the sterilization and disinfection functional resin masterbatch

[0087] According to the Guangdong Provincial Microbiology Testing Center, the antiviral activity of the sterilizing and disinfecting resin masterbatch against influenza A virus (H1N1) was 95.65%. Detailed results are shown in Table 2.

[0088] Table 2

[0089]

[0090]

[0091] Example 7: Sterilization Test of Antiviral and Sterilizing Resin Masterbatch

[0092] According to tests conducted by Guangzhou Institute of Microbiology Co., Ltd., the sterilization and disinfection functional resin masterbatch achieved kill rates of over 99.9% against Escherichia coli, 99.9% against Staphylococcus aureus, and 97.8% against Candida albicans. Detailed results are shown in Table 3.

[0093] Table 3

[0094]

[0095] The above description is merely a few embodiments of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any modifications or alterations made by those skilled in the art without departing from the scope of the technical solution of the present invention using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A sterilizing and disinfecting nonwoven fabric, characterized in that, The sterilizing and disinfecting nonwoven fabric contains sterilizing and disinfecting functional materials, which are prepared by mixing and melting resin chips and sterilizing and disinfecting functional resin masterbatch, and then spinning and web laying. The resin chip material is selected from PP polypropylene and / or PET polyester; The sterilization and disinfection functional resin masterbatch contains sterilization and disinfection functional materials; The sterilization and disinfection functional material is a porous inorganic titanium zirconium phosphate functional material. The mass content of the sterilizing and disinfecting functional material in the sterilizing and disinfecting non-woven fabric is 1-30%; The porous inorganic zirconium titanate functional material has the chemical formula Ti. n Zr (1-n) (HPO4)2, 0 < n < 1, has redox properties; The interlayer pore size of the porous inorganic titanium zirconium phosphate functional material is 50~200nm; The virus is the novel coronavirus SARS-CoV-2 and / or influenza A virus H1N1; The bacteria is at least one of Staphylococcus aureus, Candida albicans, and Escherichia coli; The porous inorganic titanium zirconium phosphate functional material is prepared by a method comprising the following steps: (b1) Add titanium precursor, zirconium precursor, phosphorus precursor, template agent and mineralizer to water in proportion, stir, and obtain initial gel; (b2) The initial gel obtained in step (b1) is transferred to a crystallization vessel and dynamically crystallized at 120~180℃ for 24~240 hours to obtain the crystallized product; (b3) The crystallized product obtained in step (b2) is centrifuged, washed with water until neutral, dried at 80~120℃, and calcined in air at 400~600℃ to obtain porous inorganic titanium zirconium phosphate functional material. The sterilizing and disinfecting nonwoven fabric is prepared by a method comprising the following steps: (a) The resin chips are heated and melted, wherein the melting temperature of PP polypropylene is 220~240℃ and the melting temperature of PET polyester is 270~280℃; (b) Add the porous inorganic titanium zirconium phosphate functional material obtained in step (b3) to the molten resin obtained in step (a), stir evenly, and then use a high-speed shear emulsifier to further mix and circulate to obtain resin slurry; (c) The resin slurry obtained in step (b) is fed into an extruder and drawn into strips to obtain strip materials; (d) After the strip material extruded in step (c) is cooled with water, it is fed into a pelletizer to obtain sterilization and disinfection function resin masterbatch; The molar ratio of the titanium precursor, zirconium precursor, phosphorus precursor, template agent, mineralizer, and water is 0.1~3.0: 0.1~3.0: 0.5~5: 0.1~3.0: 0.1~1:

100.

2. The sterilizing and disinfecting nonwoven fabric according to claim 1, characterized in that, The titanium precursor is selected from at least one of titanium chloride, tetrabutyl titanate, and tetraethyl titanate. The zirconium precursor is selected from at least one of tetraethyl zirconate, zirconium oxychloride, and zirconium nitrate. The phosphorus precursor is selected from phosphoric acid and / or ammonium phosphate; The template agent is selected from at least one of ethylenediamine, 1,3-propanediamine, and triethylamine; the mineralizing agent is selected from HF and / or NH4F.

3. The method for preparing the sterilizing and disinfecting nonwoven fabric according to claim 1, characterized in that, The preparation method includes the following steps: (a) Mix the resin chips and sterilization and disinfection functional resin masterbatch in proportion, heat and melt them and stir evenly. The melting temperature of PP polypropylene is 220~240℃ and the melting temperature of PET polyester is 270~280℃. (b) The resin slurry obtained in step (a) is fed into a screw extruder for high-temperature melt extrusion. The molten resin is fed into the spinneret by a spinneret metering pump and then extruded into fine fiber filaments through the spinneret plate. (c) The fiber filaments sprayed in step (b) are stretched by airflow and laid into a web, and then hot rolled by a rolling mill to obtain a sterilized nonwoven fabric.

4. The preparation method according to claim 3, characterized in that, The sterilizing and disinfecting nonwoven fabric can be formed into a web on its own or combined with meltblown nonwoven fabric to form a web. Including single-layer sterilization and disinfection nonwoven fabric S, sterilization and disinfection nonwoven fabric + sterilization and disinfection nonwoven fabric SS, sterilization and disinfection nonwoven fabric + meltblown nonwoven fabric + sterilization and disinfection nonwoven fabric SMS, and sterilization and disinfection nonwoven fabric + meltblown nonwoven fabric + meltblown nonwoven fabric + sterilization and disinfection nonwoven fabric SMMS composite nonwoven fabric.

5. The application of the sterilizing nonwoven fabric according to claim 1 in masks, protective clothing, medical drapes, and surgical pads.

Images