WO2021244477A1 - 铜涂覆的抗微生物过滤材料 - Google Patents

铜涂覆的抗微生物过滤材料 Download PDF

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WO2021244477A1
WO2021244477A1 PCT/CN2021/097293 CN2021097293W WO2021244477A1 WO 2021244477 A1 WO2021244477 A1 WO 2021244477A1 CN 2021097293 W CN2021097293 W CN 2021097293W WO 2021244477 A1 WO2021244477 A1 WO 2021244477A1
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filter
filter material
present
copper
coating layer
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PCT/CN2021/097293
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English (en)
French (fr)
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丁浩旻
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南京鼎卫空气净化有限公司
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Publication of WO2021244477A1 publication Critical patent/WO2021244477A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1214—Chemically bonded layers, e.g. cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/02—Loose filtering material, e.g. loose fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
    • B01D46/0028—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions provided with antibacterial or antifungal means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/30—Particle separators, e.g. dust precipitators, using loose filtering material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0442—Antimicrobial, antibacterial, antifungal additives

Definitions

  • the invention relates to a filter material, in particular to a copper-coated filter material with a composite filter filament structure.
  • Inorganic fibers include glass fibers, ceramic fibers, and so on.
  • Air filter materials not only need to have high filtration efficiency and long service life; at the same time, for the filtration of breathing air, the filter materials must be non-toxic and have no health risks. More importantly, they must have good sterilization during the service life. The ability to kill viruses and microorganisms. With the emergence of these requirements, composite filter materials have become a development trend.
  • the early composite filter materials were simple laminated composites, such as thermal bonding of different non-woven fabrics under a certain temperature and pressure.
  • Patent US20150258480A1 describes a composite filter material in which an antibacterial compound containing zinc is superimposed in an air filter material.
  • Patent US20080302713A1 also describes an air filter structure with an antimicrobial layer superimposed.
  • the existing air filter materials often have the disadvantages that it takes a long time to kill microorganisms, and/or the effect of killing microorganisms is insufficient. Therefore, there is still a need to develop new filter materials in order to achieve fast, efficient and long-lasting killing of microorganisms and a broad antimicrobial spectrum.
  • the present invention develops a filter material that can achieve rapid, efficient, long-lasting and broad antimicrobial spectrum.
  • the present invention provides a filter material, characterized in that the filter material includes an inner filter core material and a coating layer covering the outer layer of the filter core material, wherein the coating layer is selected from the following One or more of: copper, silver, zinc, gold, and alloys of one or more of them.
  • the cladding layer is copper.
  • the coating layer is evenly distributed or non-uniformly distributed on the outer layer of the filter core material.
  • the thickness of the coating layer is 0.001 ⁇ m-500 ⁇ m, preferably 0.001 ⁇ m-300 ⁇ m, preferably 0.001-100 ⁇ m, preferably 0.1-1 ⁇ m.
  • the filter material of the present invention has a mesh structure woven by a plurality of filter core materials interlaced with each other.
  • the filter element is selected from one or more of the following: polyester, polyamide, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, polyethersulfone (PES), cellulose acetate Element (CA), mixed cellulose ester (MCE), nitrocellulose (NC), polyvinylidene fluoride (PVDF), nylon (NV), expanded polytetrafluoroethylene (EPTEF), glass fiber and ceramic fiber .
  • the filter element is in the shape of a filter filament.
  • the diameter of the filter filament ranges from 0.05 ⁇ m to 500 ⁇ m, preferably from 0.05 ⁇ m to 300 ⁇ m, preferably from 0.05 ⁇ m to 100 ⁇ m, preferably from 0.05 ⁇ m to 50 ⁇ m, preferably from 0.01 ⁇ m to 30 ⁇ m, preferably from 0.01 ⁇ m to 10 ⁇ m, It is preferably 0.1 ⁇ m to 1 ⁇ m.
  • the coating layer is copper, and the average copper content in the coating layer is 300mg / m 2 or more, preferably 300mg / m 2 -1000mg / m 2 , preferably 300mg / m 2 -700mg /m 2 , preferably 300mg/m 2 -500mg/m 2 , preferably 300mg/m 2 -400mg/m 2 , preferably 300mg/m 2 -350mg/m 2 , preferably 300mg/m 2 -320mg/m 2 , preferably 300mg /m 2 .
  • the coating layer is connected to the outer layer of the filter core material by a chemical bond, for example, is connected to the outer layer of the filter core material by a coordination bond.
  • the present invention provides the use of the filter material of the present invention in the preparation of a filtering product that kills microorganisms.
  • the present invention provides a filter article comprising the filter material of the present invention.
  • the microorganisms are bacteria, such as Escherichia coli and Staphylococcus aureus; and viruses, such as enterovirus EV71, Coxsackie virus CA16, and coronavirus.
  • the filter product includes a mask filter element, a purifier filter element, an air conditioner filter element, and a vent filter element.
  • the filtration article may further comprise other filtering material, such as activated carbon, silver-based filter material, filter material and a zinc-based TiO 2 based filter material.
  • other filtering material such as activated carbon, silver-based filter material, filter material and a zinc-based TiO 2 based filter material.
  • the filter material of the present invention can achieve a rapid killing effect for microorganisms as low as 5 minutes, and can maintain a long-term effect for a long time. Moreover, the filtering material of the present invention can eliminate microorganisms with an efficiency of over 99%. In addition, the filter material of the present invention is suitable for a variety of microorganisms including bacteria and viruses, and has a broad antimicrobial spectrum.
  • Figure 1 Schematic diagram of the structure of the filter material of the present invention.
  • the number 1 represents the filter core material
  • the number 2 is the coating layer covering the outer layer of the filter core material.
  • Figure 2 A cross-sectional view of the filter material of the present invention.
  • A The coating layer is evenly distributed on the outer layer of the filter element; and B: The coating layer is unevenly distributed on the outer layer of the filter element.
  • the number 1 represents the filter core material
  • the number 2 is the coating layer covering the outer layer of the filter core material.
  • Figure 3 Microscopic examination results of a filter material sample with a copper coating amount of 300 mg/m 2 of the present invention. As shown in the figure, the copper of the present invention is uniformly and continuously coated on the outer layer of the filter core material.
  • the present invention provides a filter material.
  • Figure 1 is a schematic diagram of the structure of the filter material of the present invention.
  • the filter material of the present invention is made by interlacing multiple filter core materials.
  • the filter material of the present invention has a network structure formed by interlacing a plurality of filter core materials.
  • the filter material of the present invention includes a mesh structure woven by a plurality of filter core materials interlaced with each other, and a coating layer covering the outer layer of the filter core material.
  • the filter material of the present invention can very well combine the functions of the filter core material and the material with the effect of killing microorganisms. While the filter element has the interception function, it can also efficiently and quickly kill the intercepted microorganisms, effectively preventing the breeding of microorganisms in the air filter, and entering the clean air with the airflow, causing the spread of diseases.
  • the filter material of the present invention includes an inner filter core material (1) and a coating layer (2) covering the outer layer of the filter core material (1).
  • the filter element can be a filter material commonly used in the field.
  • the filter element is selected from one or more of the following: polyester, polyamide, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, polyethersulfone (PES), cellulose acetate Element (CA), mixed cellulose ester (MCE), nitrocellulose (NC), polyvinylidene fluoride (PVDF), nylon (NV), expanded polytetrafluoroethylene (EPTEF), glass fiber and ceramic fiber .
  • the coating layer may be a metal layer, especially a metal known in the art that has the effect of killing microorganisms.
  • the coating layer is selected from one or more of the following: copper, silver, zinc, gold, and alloys of one or more of them.
  • the cladding layer is copper. Without being bound by any theory, the presence of copper can denature the proteins of microorganisms including bacteria and viruses. Therefore, by using copper in elementary form as the coating material, the filter material of the present invention can kill microorganisms.
  • Figure 2 is a cross-sectional view of a filter element in the filter material of the present invention.
  • the filter element of the present invention can be in the shape of a filter filament, and the cross-section of the filter filament can be any shape, including but not limited to a circle, an ellipse, a rectangle, a diamond, a trapezoid, and the like.
  • the filter element of the present invention is in the shape of a filter filament.
  • the filter element of the present invention is in the shape of a filter filament with a circular cross-section.
  • the coating layer (2) can be uniformly distributed on the outer layer of the filter core material (1), or the coating layer (2) can be unevenly distributed on the outer layer of the filter core material (1).
  • the coating layer is evenly distributed or non-uniformly distributed on the outer layer of the filter core material.
  • the coating layer is connected to the outer layer of the filter core material by a chemical bond.
  • the coating layer is connected to the outer layer of the filter core material by a coordination bond.
  • the coating layer is deposited on the outer layer of the filter core material by a vapor deposition method.
  • the inventor of the present invention believes that by adopting a coating layer connected with the filter core material, instead of mixing or immersing the material with antimicrobial effect such as metal with the filter core material, the coating layer can be strengthened. It is fixed on the surface of the filter element and can fully contact the target microorganisms, thereby greatly improving the effect of killing microorganisms.
  • a magnetron sputtering method may be used to connect the coating layer and the filter core material.
  • a chemical coordination method may be used to connect the coating layer and the filter element.
  • the coating layer and the filter core material can be connected by a vapor deposition method.
  • the coating layer and the filter core material can be connected by a liquid phase coating method.
  • the present invention can also reduce the residue of harmful chemicals in the production process by connecting the filter core material with the coating layer.
  • the diameter of the filter filament ranges from 0.05 ⁇ m to 500 ⁇ m, preferably from 0.05 ⁇ m to 300 ⁇ m, preferably from 0.05 ⁇ m to 100 ⁇ m, preferably from 0.05 ⁇ m to 50 ⁇ m, preferably from 0.01 ⁇ m to 30 ⁇ m, preferably from 0.01 ⁇ m to 10 ⁇ m, It is preferably 0.1 ⁇ m to 1 ⁇ m.
  • the thickness of the coating layer is 0.001 ⁇ m-500 ⁇ m, preferably 0.001 ⁇ m-300 ⁇ m, preferably 0.001-100 ⁇ m, preferably 0.1-1 ⁇ m.
  • the material with antimicrobial effect contained in the coating layer is metal
  • the average content of the metal is at least 300 mg/m 2 , preferably 300 mg/m 2 -1000 mg/m 2 , preferably 300mg/m 2 -700mg/m 2 , preferably 300mg/m 2 -500mg/m 2 , preferably 300mg/m 2 -400mg/m 2 , preferably 300mg/m 2 -350mg/m 2 , preferably 300mg/m 2 -320mg /m 2 , preferably 300 mg/m 2 .
  • the metal is one or more selected from the group consisting of copper, silver, zinc, gold, and an alloy of one or more of them.
  • the metal is copper.
  • the coating layer of the present invention is copper, and the average copper content of the coating layer is at least 300 mg/m 2 , preferably 300 mg/m 2 -1000 mg/m 2 , preferably 300 mg/m 2- 700mg/m 2 , preferably 300mg/m 2 -500mg/m 2 , preferably 300mg/m 2 -400mg/m 2 , preferably 300mg/m 2 -350mg/m 2 , preferably 300mg/m 2 -320mg/m 2 , preferably 300mg/m 2 .
  • the present invention proves that when the average copper content of the coating layer is greater than 300 mg/m 2 , the filter material of the present invention can achieve a rapid killing effect for microorganisms as low as 5 minutes, and it is still excellent when contacted with microorganisms for up to 18 hours.
  • the bactericidal effect, and the killing efficiency is as high as 99%.
  • the present invention also proves that the filter material of the present invention can achieve long-term sterilization, and the sterilization effect in 3 months is still above 90%.
  • the filter material of the present invention has the effect of quickly killing microorganisms within 5 minutes. In one embodiment, the filter material of the present invention has an effect of killing microorganisms of greater than 99%. In one embodiment, the filter material of the present invention can last up to 3 months, and still has at least more than 90% of the effect of killing microorganisms such as bacteria after 3 months.
  • the filter material of the present invention can have a good killing effect on microorganisms including bacteria and viruses, and therefore has a wide antimicrobial spectrum. Therefore, in another aspect, the present invention provides the use of the filter material of the present invention in the preparation of a filter product that kills microorganisms.
  • the microorganisms include bacteria, fungi, and viruses.
  • the bacteria include, but are not limited to, Staphylococcus, Pseudobacterium, Escherichia, Candida, Salmonella, Streptococcus (Streptococcus), Haemophilus, Neisseria, etc.
  • the bacteria are selected from one or more of the following: Staphylococcus aureus, Pseudomonas aeruginosa, E. coli, Candida albicans , Salmonella enteritidis, Salmonella typhi, Streptococcus pneumoniae, Haemophilus influenzae and Neisseria gonorrheoeae.
  • the fungus includes but is not limited to mold and yeast. In one embodiment, the fungus is Aspergillus or Penicillium.
  • the virus includes, but is not limited to, influenza virus, hepatitis virus, coronavirus, adenovirus, rhinovirus, enterovirus, and the like.
  • the microorganisms are bacteria, such as Escherichia coli and Staphylococcus aureus; and viruses, such as enterovirus EV71, Coxsackie virus CA16, and coronaviruses such as novel coronavirus.
  • the present invention provides a filter article containing the filter material of the present invention.
  • Filter products that can use the filter material of the present invention include, but are not limited to, personal protective equipment, such as masks, etc.; and air filtration devices, such as air-conditioning filters for vehicles, such as car air-conditioning filters, train air-conditioning filters, airplane air-conditioning filters, and household air-conditioning filters , Public places such as buildings, such as air-conditioning filters in hospitals, etc., and air outlet filters in public places such as buildings.
  • the filter product containing the filter material of the present invention is an automobile air-conditioning filter element.
  • the filter product containing the filter material of the present invention is an air outlet filter element of a building.
  • the filter product containing the filter material of the present invention is a fresh air system.
  • the filter product containing the filter material of the present invention is an automobile air conditioning filter element or an automobile air filter element.
  • the filter article containing the filter material of the present invention is a medical protective clothing fabric.
  • the filter article containing the filter material of the present invention is an emergency breathing mask.
  • the filter article containing the filter material of the present invention is a shroud/body bag.
  • the filter product containing the filter material of the present invention is an air evolution system used in a laminar flow room of a hospital.
  • the filter article of the present invention may contain one or more filter materials of the present invention.
  • the filter article of the present invention may further comprise other filtering materials, such as activated carbon, silver-based filter material, filter material, zinc-based, nano and nano anionic photocatalyst such as TiO 2 nanoparticles based filter material.
  • the present invention also relates to a method for preparing the filter material of the present invention, including connecting the filter core material and the coating layer.
  • the coating layer is selected from one or more of the following: copper, silver, zinc, gold, and alloys of one or more of them.
  • the filter element is selected from one or more of the following: polyester, polyamide, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, polyethersulfone (PES), cellulose acetate Element (CA), mixed cellulose ester (MCE), nitrocellulose (NC), polyvinylidene fluoride (PVDF), nylon (NV), expanded polytetrafluoroethylene (EPTEF), organic glass fiber and ceramic fiber .
  • the coating layer is connected to the outer layer of the filter core material by a chemical bond. In one embodiment, the coating layer is connected to the outer layer of the filter core material by a coordination bond.
  • the present invention also relates to a method of preparing a filter article containing the filter material of the present invention, including placing the filter material of the present invention in the filter article.
  • the method of the present invention for preparing a filter article containing the filter material of the present invention includes placing the filter material of the present invention inside or outside the filter article.
  • the present invention includes placing the filter material of the present invention inside an air outlet of a building or an automobile air-conditioning filter element.
  • the present invention includes placing the filter material of the present invention outside the air outlet of an automobile air conditioner or the air outlet of a building. Therefore, the filter material of the present invention has a very wide range of applications.
  • the polypropylene PP material with a filter diameter of 10 microns is used as the filter material substrate, the coating material is copper, and the copper is coated on the filter material substrate by magnetron sputtering.
  • the filter substrate First, place the filter substrate into the vacuum chamber and set the transmission speed to 5m/min. In this step, the transmission speed can be adjusted due to the loss of the target material. Subsequently, the copper target is placed in place and placed in the cavity. After evacuating the vacuum chamber to 10 -4 Pa, it is filled with an inert gas of 1 Pa, which is used as a carrier for gas discharge.
  • the parameters of the film thickness meter of the magnetron sputtering instrument were set to correspond to a copper equivalent of 250 mg/m 2 copper coating thickness. Turn on the instrument to coat the copper on the polypropylene PP substrate so that the copper and the substrate are connected by chemical bonds. Observe under microscope to ensure uniform coating. Finally, a polypropylene PP substrate coated with a 250 mg/m 2 copper coating layer (Sample 1) was obtained.
  • a polyester PE material with a filter filament diameter of 10 microns is used as the filter material substrate, and the coating material is copper.
  • the copper is coated on the filter material substrate by magnetron sputtering.
  • the polypropylene PP material with a filter diameter of 10 microns is used as the filter material substrate, the coating material is copper, and the copper is coated on the filter material substrate by magnetron sputtering.
  • the method steps are as described above, and the difference is that the parameters of the film thickness meter are set to correspond to the copper equivalent of 300 mg/m 2 copper coating thickness. Turn on the instrument to coat copper on the polypropylene PP substrate. Observe under microscope to ensure uniform coating. To obtain a polypropylene PP substrate coated with a 300 mg/m 2 copper coating layer (Sample 3).
  • the parameters of the film thickness meter are set to correspond to a copper equivalent of 300 mg/m 2 copper coating thickness.
  • the instrument was turned on, and copper coating was performed on the polypropylene PP substrate to obtain a polyester PE substrate coated with a 300 mg/m 2 copper coating layer (Sample 4).
  • a chemical coordination method is used to coat copper.
  • the polypropylene PP material with a filter diameter of 10 microns is also used as the filter material base material.
  • the polypropylene PP material is modified.
  • the modification method can be found in (Steigerung der von isotaktischem Polypropylen Anlagen strokes, Michaela.Universitaet Bayreuth(Germany),ProQuest Dissertations Publishing,2018.27600475; Otto Schwarz:Kunststoff ambience.Vogel,Würzburg 2002(7.Hommel.).ISBN 3802319176 3;Hans Domininghaus:Die Kunststoffe und ihlin-Heidenschaften.
  • the testing unit is the Antimicrobial Material Testing Center of the Technical Institute of Physics and Chemistry of the Chinese Academy of Sciences.
  • test microorganisms used Escherichia coli (ATCC 25922) and Staphylococcus aureus (Staphylococcus aureus; ATCC6538).
  • the samples submitted for inspection are cut to a size of 18mm x 18mm.
  • the first group has no test bacteria, or only a few test bacteria colonies grow.
  • the second group has more test colonies than the first group, but less than the third, 4th, and 5th groups, and meets the requirements.
  • Groups 3, 4, and 5 have similar growth of test bacteria, and between 1x 10 4 -9x 10 4 cfu/tablet, the error rate of the number of colonies between the groups should not exceed 15%.
  • test organism used was the slant culture Sin PBS to prepare bacterial suspension (concentration required is: with 100 ⁇ L drops on the control samples, bacteria count is recovered 1x 10 4 -9x 10 4 cfu / plate).
  • test data are as follows:
  • the filter material with a copper coating amount of 300 mg/m 2 of the present invention can achieve an antibacterial/bactericidal effect of >99%, which far exceeds the requirement of a sterilization rate of ⁇ 90% specified in the GB15979-2002 standard. Moreover, the 300 mg/m 2 copper coating filter material of the present invention can quickly achieve this high antibacterial/bactericidal rate, and the required time is as short as 5 minutes.
  • the testing unit is the Antimicrobial Material Testing Center of the Technical Institute of Physics and Chemistry of the Chinese Academy of Sciences.
  • test data are as follows:
  • the antiviral effect of sample 3 was tested.
  • the testing unit is Guangzhou Huyan Institute Medical Technology Co., Ltd.
  • the anti-virus effect test method is as follows:
  • test samples are cut for use, and the toxicity of the test samples to cells is evaluated.
  • test sample was reacted with the virus suspension for 18 hours, the sample was recovered to detect the disease, and the experiment was set as a blank control.
  • test sample has no toxic effect on Vero cells, and the cells grow well.
  • test sample reacts with enterovirus EV71 and Coxsackie virus CA16 suspension for 18 hours, and the test sample has a certain killing effect on enterovirus EV71 and Coxsackie virus CA16 ( Table 4).
  • the filter material of the present invention also has a good killing effect on viruses, and the virus killing rate in 18 hours reaches more than 99%.
  • the filter material of the present invention selects sample 3 for experiment.
  • the control filter materials used commercially available copper-containing filter materials and nano-silver-containing filter materials. Test the antibacterial and antiviral effects of the above filter materials against Escherichia coli and coronavirus GX_P2V in 5 minutes and 18 hours, respectively.
  • the test method refers to the foregoing Examples 3-5.
  • the filter material of the present invention has an excellent killing effect on both bacteria and viruses compared to the copper-containing filter material and the nano-silver-containing filter material. Moreover, the filter material of the present invention can not only achieve a rapid antibacterial effect, but also the antibacterial effect can last for a long time.
  • the above experiment did not end after 18 hours.
  • the sample 3 was transferred and attached to the air outlet of the air filter of an office building and kept for 3 months, and then the sterilization effect was measured.
  • the parallel control used ordinary PP material that did not contain the copper coating layer of the present invention as the filter material. Refer to Example 3 for the measurement method.
  • the filter material of the present invention can achieve long-acting sterilization, the sterilization effect can be maintained for at least 3 months, and the sterilization effect for 3 months is still above 90%, which meets the requirement of ⁇ 90% in the national GB15979-2002 standard.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Filtering Materials (AREA)

Abstract

本发明涉及一种过滤材料，所述过滤材料包括内部的过滤芯材和包覆在所述过滤芯材外层的包覆层，其中所述包覆层选自以下的一种或多种：铜、银、锌、金以及他们中一种或多种的合金。本发明还涉及包括此过滤材料的过滤制品。本发明的过滤材料具有快速、高效和持久杀灭微生物，以及抗微生物谱广泛的效果。

Description

铜涂覆的抗微生物过滤材料 技术领域
本发明涉及过滤材料，具体涉及具有复合滤丝结构的铜涂覆的过滤材料。
背景技术
随着当代人们对大气和室内空气质量的日益重视，空气过滤材料的技术提高要求不断增加。1940年玻璃纤维空气材料获得美国专利。之后随着非织造工业的发展，出现了各种化纤材料做成的空气过滤材料，如聚酯(PET)，聚酰胺，聚丙烯(PP)，聚苯硫醚(PPS)，聚四氟乙烯(PTFE)等等，无机纤维有玻璃纤维，陶瓷纤维等等。
当前对于空气过滤材料的要求越来越高，越来越多样化。空气过滤材料不仅需要有很高的过滤效能，长的使用寿命；同时针对于呼吸空气的过滤，过滤材料要求无毒，无健康风险，更重要的是要在使用寿命期限内有很好的杀菌杀病毒，杀灭微生物的能力。随着这些要求的出现，复合滤料成为发展的趋势。早期的复合滤料为简单的叠制复合，如将不同的非织造布在一定温度和压力的作用下热粘合而成。
然而，随着人们对呼吸空气质量的要求越来越高，现在对于空气过滤材料的要求已经不满足于对于颗粒的拦截和对有害气体的去除。更加重要的是对细菌病毒等有害微生物的去除，阻隔疾病的传播。因此产生了多种形式的复合滤材。
专利US20150258480A1描述了在空气滤材中，叠加了含锌的抗菌化合物的复合滤材。专利US20080302713A1也描述了一种叠加了抗微生物层的空气滤材结构。还有文献将TiO 2光催化剂膜叠加复合在空气滤材上面，或者将纳米银颗粒添加到滤材表面达到杀灭微生物的功效。
但是，现有的空气滤材往往存在杀灭微生物需要较长时间，和/或杀灭微生物效果不足等缺陷。因此，依旧需要开发新型过滤材料，以盼实现快 速、高效和长效持久杀灭微生物，以及抗微生物谱广泛的效果。
发明内容
为了解决现有技术中存在的问题，本发明开发了一种可以实现快速、高效、持久且抗微生物谱广泛的过滤材料。
一方面，本发明提供了一种过滤材料，其特征在于所述过滤材料包括内部的过滤芯材和包覆在所述过滤芯材外层的包覆层，其中所述包覆层选自以下的一种或多种：铜、银、锌、金以及他们中一种或多种的合金。
在一个实施方式中，所述包覆层为铜。
在一个实施方式中，所述包覆层均匀分布或非均匀分布在所述过滤芯材外层。
在一个实施方式中，所述包覆层的厚度为0.001μm-500μm，优选0.001μm-300μm，优选0.001-100μm，优选0.1-1μm。
在一个实施方式中，本发明的过滤材料具有由多根过滤芯材相互交错所编织成的网状结构。
在一个实施方式中，所述过滤芯材选自包括以下的一种或多种：聚酯、聚酰胺、聚丙烯、聚苯硫醚、聚四氟乙烯、聚醚砜(PES)、醋酸纤维素(CA)、混合纤维素酯(MCE)、硝酸纤维素(NC)、聚偏二氟乙烯(PVDF)、尼龙(NV)、膨体聚四氟乙烯(EPTEF)、有玻璃纤维和陶瓷纤维。
在一个实施方式中，所述过滤芯材为滤丝形状。
在一个实施方式中，所述滤丝的直径的范围为0.05μm-500μm，优选0.05μm-300μm，优选0.05μm-100μm，优选0.05μm-50μm，优选0.01μm-30μm，优选0.01μm-10μm，优选0.1μm-1μm。
在一个实施方式中，所述包覆层为铜，且所述包覆层的平均含铜量在300mg/m 2以上，优选300mg/m 2-1000mg/m 2，优选300mg/m 2-700mg/m 2，优选300mg/m 2-500mg/m 2，优选300mg/m 2-400mg/m 2，优选300mg/m 2-350mg/m 2，优选300mg/m 2-320mg/m 2，优选300mg/m 2。
在一个实施方式中，所述包覆层通过化学键与所述过滤芯材外层连接，例如通过配位键与所述过滤芯材外层连接。
另一方面，本发明提供本发明的过滤材料在制备杀灭微生物的过滤制 品中的用途。
又一方面，本发明提供了包含本发明过滤材料的过滤制品。
在一个实施方式中，所述微生物为细菌，例如大肠杆菌和金黄色葡萄球菌；和病毒，例如肠道病毒EV71、柯萨奇病毒CA16和冠状病毒。
在一个实施方式中，所述过滤制品包括口罩滤芯、净化器滤芯、空调滤芯和通风口滤芯。
在一个实施方式中，所述过滤制品可以进一步包括其它过滤材料，例如活性炭、银基过滤材料、锌基过滤材料和TiO 2基过滤材料。
本发明的过滤材料对于微生物可以实现低至5分钟的快速杀灭效果，并可保持长效保持很久。而且本发明的过滤材料对于微生物的消灭效率可以达到99％以上。此外，本发明的过滤材料适用于包括细菌和病毒在内的多种微生物，具有广泛的抗微生物谱。
附图说明
图1：本发明过滤材料的结构示意图。
附图标记：数字①代表过滤芯材，数字②为包覆在所述过滤芯材外层的包覆层。
图2：本发明过滤材料的截面图。
A：包覆层均匀分布在过滤芯材外层；和B：包覆层非均匀分布在过滤芯材外层。
附图标记：数字①代表过滤芯材，数字②为包覆在所述过滤芯材外层的包覆层。
图3：本发明300mg/m 2铜涂覆量的滤材样品的显微镜镜检结果。如图所示，本发明的铜十分均匀且连续地包覆在过滤芯材外层。
具体实施方式
一方面，本发明提供了一种过滤材料。图1是本发明过滤材料的结构示意图。
如图1所示，本发明的过滤材料由多根过滤芯材相互交错编制制成。在一个实施方式中，本发明的过滤材料具有由多根过滤芯材相互交错所编 织成的网状结构。在一个实施方式中，本发明过滤材料包括由多根过滤芯材相互交错所编织成的网状结构，以及包覆在过滤芯材外层的包覆层。本发明的过滤材料可以非常好地将过滤芯材和具有杀灭微生物效果的材料的功能相结合。过滤芯材在产生拦截功能的同时，也可以高效快速的杀灭所拦截的微生物，有效防止微生物在空气过滤器中的滋生繁殖，并随着气流进入到清洁空气中，而造成疾病的传播。
如图1所示，本发明的过滤材料包括内部的过滤芯材(1)和包覆在过滤芯材(1)外层的包覆层(2)。所述过滤芯材可以为本领域常用的过滤材料。在一个实施方式中，所述过滤芯材选自包括以下的一种或多种：聚酯、聚酰胺、聚丙烯、聚苯硫醚、聚四氟乙烯、聚醚砜(PES)、醋酸纤维素(CA)、混合纤维素酯(MCE)、硝酸纤维素(NC)、聚偏二氟乙烯(PVDF)、尼龙(NV)、膨体聚四氟乙烯(EPTEF)、有玻璃纤维和陶瓷纤维。所述包覆层可以为金属层，特别是本领域已知的具有杀灭微生物效果的金属。在一个实施方式中，所述包覆层选自以下的一种或多种：铜、银、锌、金以及他们中一种或多种的合金。在一个实施方式中，所述包覆层为铜。不受限于任何理论，铜的存在可以使得包括细菌和病毒在内的微生物的蛋白质发生变性。因此，通过采用单质形式的铜作为包覆材料，本发明的过滤材料可以实现对于微生物的杀灭。
图2是本发明过滤材料中过滤芯材的截面图。本发明的过滤芯材可以为滤丝形状，且所述滤丝的截面可以为任何形状，包括但不限于圆形、椭圆形、矩形、菱形、梯形等。在一个实施方式中，本发明的过滤芯材为滤丝形状。在一个实施方式中，本发明的过滤芯材为具有圆形截面的滤丝形状。
如图2A所示，包覆层(2)可以均匀分布在过滤芯材(1)外层，或者包覆层(2)可以非均匀分布在过滤芯材(1)外层。在一个实施方式中，所述包覆层均匀分布或非均匀分布在所述过滤芯材外层。在一个实施方式中，所述包覆层通过化学键与所述过滤芯材外层连接。在一个实施方式中，所述包覆层通过配位键与所述过滤芯材外层连接。在一个实施方式中，所述包覆层通过气相蒸镀的方法被沉积到所述过滤芯材外层。
不受限于任何理论，本发明发明人认为通过采用与过滤芯材连接的包 覆层，而非将具有杀灭微生物效果的材料例如金属与过滤芯材混合或浸泡，可以将包覆层牢固固定在过滤芯材表面，并使其能够与目标微生物充分接触，由此极大地提高杀灭微生物的效果。在一个实施方式中，可以采用磁控溅射的方法将包覆层与过滤芯材连接。在一个实施方式中，可以采用化学配位的方法将包覆层与过滤芯材连接。在一个实施方式中，可以采用气相蒸镀法的方法将包覆层与过滤芯材连接。在一个实施方式中，可以采用液相涂附的方法将包覆层与过滤芯材连接。此外，相比于将金属与过滤芯材混合或浸泡等方式，本发明通过将过滤芯材与包覆层连接，也可以降低生产过程的有害化学物的残留。
在一个实施方式中，所述滤丝的直径的范围为0.05μm-500μm，优选0.05μm-300μm，优选0.05μm-100μm，优选0.05μm-50μm，优选0.01μm-30μm，优选0.01μm-10μm，优选0.1μm-1μm。在一个实施方式中，所述包覆层的厚度为0.001μm-500μm，优选0.001μm-300μm，优选0.001-100μm，优选0.1-1μm。
本发明的发明人还发现，当包覆层的所含的杀灭微生物效果的材料例如金属的平均含量到达一定数值后，杀灭微生物的多方面效果可以得到极大的改善。在一个实施方式中，所述包覆层的所含的杀灭微生物效果的材料为金属，且所述金属的平均含量至少为300mg/m 2，优选300mg/m 2-1000mg/m 2，优选300mg/m 2-700mg/m 2，优选300mg/m 2-500mg/m 2，优选300mg/m 2-400mg/m 2，优选300mg/m 2-350mg/m 2，优选300mg/m 2-320mg/m 2，优选300mg/m 2。在一个实施方式中，所述金属为选自以下的一种或多种：铜、银、锌、金以及他们中一种或多种的合金。在一个实施方式中，所述金属为铜。
在一个实施方式中，本发明包覆层为铜，且所述包覆层的平均含铜量为至少为300mg/m 2，优选300mg/m 2-1000mg/m 2，优选300mg/m 2-700mg/m 2，优选300mg/m 2-500mg/m 2，优选300mg/m 2-400mg/m 2，优选300mg/m 2-350mg/m 2，优选300mg/m 2-320mg/m 2，优选300mg/m 2。本发明证实，当包覆层的平均含铜量大于300mg/m 2时，本发明过滤材料对于微生物可以实现低至5分钟的快速杀灭效果，与微生物接触长达18小时也仍然具有优异的杀菌效果，而且杀灭效率高达99％以上。
此外，本发明还证实本发明滤材可以实现长效性杀菌，3个月的杀菌效果依旧在90％以上。
在一个实施方式中，本发明滤材具有5min内的快速杀灭微生物的效果。在一个实施方式中，本发明滤材具有大于99％的杀灭微生物的效果。在一个实施方式中，本发明滤材具有可持续长达3个月，且3个月后依旧至少具有大于90％的杀灭微生物例如细菌的效果。
实验还证实本发明的过滤材料对于包括细菌和病毒在内的微生物均可以起到很好的杀灭效果，因此具有广泛的抗微生物谱。因此，另一方面，本发明提供本发明的过滤材料在制备杀灭微生物的过滤制品中的用途。
在一个实施方式中，所述微生物包括细菌、真菌和病毒。在一个实施方式中，所述细菌包括但不限于葡萄球菌属(Staphylococcus)、脓杆菌属(Pseudobacterium)、埃希菌属(Escherichia)、念珠球菌属(Candida)、沙门氏菌(Salmonella)、链球菌属(Streptococcus)、嗜血杆菌属(Haemophilus)、双球菌属(Neisseria)等。在一个实施方式中，所述细菌选自以下一种或多种：金黄色葡萄球菌(Staphylococcus aureus)、绿脓杆菌(Pseudomonas aeruginosa)、大肠杆菌(E.coli)、白色念珠球菌(Candida albicans)、肠炎沙门氏菌(Salmonella enteritidis)、沙门氏伤寒菌(Salmonella typhi)、肺炎链球菌(Streptococcus pneumoniae)、流感杆菌(Haemophilus influenzae)和淋病双球菌(Neisseria gonorrheoeae)。
在一个实施方式中，所述真菌包括但不限于霉菌和酵母菌。在一个实施方式中，所述真菌为曲霉菌属(Aspergillus)或青霉菌属(Penicillium)。在一个实施方式中，所述病毒包括但不限于流感病毒、肝炎病毒、冠状病毒、腺病毒、鼻病毒、肠道病毒等。在一个实施方式中，所述微生物为细菌，例如大肠杆菌和金黄色葡萄球菌；和病毒，例如肠道病毒EV71、柯萨奇病毒CA16和冠状病毒如新型冠状病毒。
又一方面，本发明提供了一种包含本发明过滤材料的过滤制品。可以使用本发明过滤材料的过滤制品包括但不限于个人防护用品，例如口罩等；以及空气过滤装置，例如交通工具的空调滤芯，例如汽车空调滤芯、火车空调滤芯、飞机空调滤芯，以及家用空调滤芯、公共场所如建筑物，例如医院的空调滤芯等，公共场所如建筑物的空气出风口滤芯。在一个实施方 式中，包含本发明过滤材料的过滤制品为汽车空调滤芯。在一个实施方式中，包含本发明过滤材料的过滤制品为建筑物的空气出风口滤芯。在一个实施方式中，包含本发明过滤材料的过滤制品为新风系统。在一个实施方式中，包含本发明过滤材料的过滤制品为汽车空调滤芯或汽车空气滤芯。在一个实施方式中，包含本发明过滤材料的过滤制品为医用防护服面料。在一个实施方式中，包含本发明过滤材料的过滤制品为急救呼吸面罩。在一个实施方式中，包含本发明过滤材料的过滤制品为裹尸布/裹尸袋。在一个实施方式中，包含本发明过滤材料的过滤制品为医院层流室所用空气进化系统。
在一个实施方式中，本发明的过滤制品可以包含一层或多种本发明的过滤材料。在一个实施方式中，本发明的过滤制品可以进一步包括其它过滤材料，例如活性炭、银基过滤材料、锌基过滤材料、纳米阴离子和纳米光触媒如纳米TiO 2基过滤材料。
再一方面，本发明还涉及制备本发明过滤材料的方法，包括将过滤芯材与包覆层连接。在一个实施方式中，所述包覆层选自以下的一种或多种：铜、银、锌、金以及他们中一种或多种的合金。在一个实施方式中，所述过滤芯材选自包括以下的一种或多种：聚酯、聚酰胺、聚丙烯、聚苯硫醚、聚四氟乙烯、聚醚砜(PES)、醋酸纤维素(CA)、混合纤维素酯(MCE)、硝酸纤维素(NC)、聚偏二氟乙烯(PVDF)、尼龙(NV)、膨体聚四氟乙烯(EPTEF)、有机玻璃纤维和陶瓷纤维。在一个实施方式中，所述包覆层通过化学键与所述过滤芯材外层连接。在一个实施方式中，所述包覆层通过配位键与所述过滤芯材外层连接。
再一方面，本发明还涉及制备包含本发明过滤材料的过滤制品的方法，包括将本发明的过滤材料置于过滤制品中。在一个实施方式中，本发明的制备包含本发明过滤材料的过滤制品的方法包括将本发明的过滤材料置于过滤制品内部或外部。在一个实施方式中，本发明包括将本发明的过滤材料置于建筑物的空气出风口或汽车空调滤芯的内部。在一个实施方式中，本发明包括将本发明的过滤材料置于汽车空调出风口或者建筑物的空气出风口外侧。因此，本发明的过滤材料具有十分广泛的应用范围。
本发明的特定实施方案现在将通过以下非限制性实施例进行描述。
实施例
实施例1 250mg/m 2铜涂覆量的滤材的制备(样品1-2)
采用滤丝直径10微米的聚丙烯PP材料作为滤材基材，涂覆材料为铜，采用磁控溅射方式将铜涂覆到滤材基材上。
首先，将滤材基材放置入真空腔，设置传动速度为5m/min。此步骤中，传动速度可以因靶材损耗不同而有调整。随后，将铜靶材入位，置入腔中。将真空腔抽真空到10 -4Pa后，充入1Pa的惰性气体Ar，以作为气体放电的载体。
设置磁控溅射仪器的膜厚仪参数。将膜厚仪参数设定为对应于铜当量为250mg/m 2铜涂覆厚度。开启仪器，进行聚丙烯PP基材上铜的涂覆，使得铜与基材以化学键相连接。显微镜镜检观察以确保涂覆均匀。最终获得涂覆有250mg/m 2铜涂覆层的聚丙烯PP基材(样品1)。
同时，使用滤丝直径10微米的聚酯PE材料作为滤材基材，涂覆材料为铜，采用磁控溅射方式将铜涂覆到滤材基材上。
方法步骤如上所述，制备涂覆有250mg/m 2铜涂覆层的聚酯PE基材(样品2)。
实施例2 300mg/m 2铜涂覆量的滤材的制备(样品3-5)
采用滤丝直径10微米的聚丙烯PP材料作为滤材基材，涂覆材料为铜，采用磁控溅射方式将铜涂覆到滤材基材上。
方法步骤如上所述，区别在于将膜厚仪参数设定为对应于铜当量为300mg/m 2铜涂覆厚度。开启仪器，进行聚丙烯PP基材上铜的涂覆。显微镜镜检观察以确保涂覆均匀。以获得涂覆有300mg/m 2铜涂覆层的聚丙烯PP基材(样品3)。
使用同样方法，将滤材基材更换为滤丝直径10微米的聚酯PE材料。同样将膜厚仪参数设定为对应于铜当量为300mg/m 2铜涂覆厚度。开启仪器，进行聚丙烯PP基材上铜的涂覆，以获得涂覆有300mg/m 2铜涂覆层的聚酯PE基材(样品4)。
在另一方法中，使用化学配位法来涂覆铜。同样采用滤丝直径10微米的聚丙烯PP材料作为滤材基材。首先，对聚丙烯PP材料进行改性，改性 方法可以参见(Steigerung der
Figure PCTCN2021097293-appb-000001
von isotaktischem Polypropylen durch Kontrolle der Morphologie mittels 1,3,5-Benzoltrisamiden；
Figure PCTCN2021097293-appb-000002
Michaela.Universitaet Bayreuth(Germany),ProQuest Dissertations Publishing,2018.27600475；Otto Schwarz:Kunststoffkunde.Vogel,Würzburg 2002(7.Aufl.).ISBN 3802319176 3；Hans Domininghaus:Die Kunststoffe und ihre Eigenschaften.Springer,Berlin-Heidelberg 2005(6.Aufl.).ISBN 3-540-21410-0)。随后加入涂覆材料为铜使结合到其与改性的聚丙烯PP材料的表面，使得铜与基材以配位键相连接。控制涂覆材料铜的加入量，以确保获得涂覆有300mg/m 2铜涂覆层的聚丙烯PP基材(样品5)。
实施例3 样品3-5的抗菌效果的检测-1
对样品3-5的抗菌效果进行测试。测试单位为中国科学院理化技术研究所抗菌材料检测中心。
测试微生物采用大肠杆菌(Escherichia coli；ATCC 25922)和金黄色葡萄球菌(Staphylococcus aureus；ATCC6538)。
抗菌效果测试方法如下：
送检样品剪裁为18mm x 18mm大小。
1中和剂鉴定试验
依据中国人民共和国卫生部GB15979-2002标准，进行杀菌性能测试必须通过以下中和剂鉴定试验。
1.1试验分组
1)染菌样片+5mL PBS
2)染菌样片+5mL中和剂(生理盐水)
3)染菌对照片+5mL中和剂
4)样片+5mL中和剂+染菌对照片
5)染菌对照片+5mL PBS
6)同批次PBS
7)同批次中和剂
8)同批次培养基
1.2评价规定
1)第1组无试验菌，或仅有极少数试验菌菌落生长。
2)第2组有较第1组为多，但较第3、4、5组为少的试验菌落生长，并符合要求。
3)第3、4、5组有相似量试验菌生长，并在1x 10 4-9x 10 4cfu/片之间，其组间菌落数误差率应不超过15％。
4)第6-8组无菌生长。
5)连续3次试验取得合格评价。
3.2杀菌试验
3.2.1操作步骤
将试验菌斜面培养物用PBS冼下，制成菌悬液(要求的浓度为：用100μL滴于对照样片上，回收菌数为1x 10 4-9x 10 4cfu/片)。
取被试样片2.0cm x 3.0cm)和对照样片(与试样同质材料，同等大小，但不含抗菌材料，且经灭菌处理)各4片，分成4组置于4个灭菌平皿内。
取上述菌悬液，分别在每个被试样片和对照样片上滴加100μL均匀涂布，开始计时，作用5min，用无菌镊分別将样片投入含5mL相应中和剂的试管内，充分混匀，作适当稀释，然后取其中2-3个稀释度，分别吸取0.5mL，置于两个平皿，用凉至40-45℃的营养琼脂培养基15mL作倾注，转动平皿，使其充分均匀，琼脂凝固后翻转平板，35±2℃培养48h，作活菌菌落计数。试验重复3次，按下式计算杀菌率：
X3＝(A-B)/A x 100％
X3＝杀菌率％；A＝对照样品平均菌落数；B＝被试样品平均菌落数。
检测数据如下：
表1
Figure PCTCN2021097293-appb-000003
表2
Figure PCTCN2021097293-appb-000004
基于上述结果可知，本发明的300mg/m 2铜涂覆量的滤材可以实现>99％的抗菌/杀菌效果，此效果远超过GB15979-2002标准中规定的≥90％的杀菌率要求。而且，本发明的300mg/m 2铜涂覆量的滤材可以快速地实现此高抗菌/杀菌率，所需的时间短至仅需5min。
实施例4 样品1-2的抗菌效果的检测-2
采用与实施例3同样的方法，对样品1-2的抗菌效果进行测试。测试单位为中国科学院理化技术研究所抗菌材料检测中心。
检测数据如下：
表3
Figure PCTCN2021097293-appb-000005
基于上述结果可知，当使用250mg/m 2铜涂覆量的滤材时，依旧可以达到99％抑菌率。但是，与使用300mg/m 2铜涂覆量的滤材相比，使用250mg/m 2铜涂覆量的滤材达到99％抑菌率所需的时间大大增加。
实施例5 本发明滤材的抗病毒效果
对样品3的抗病毒效果进行测试。测试单位为广州呼研所医药科技有限公司。抗病毒效果测试方法如下：
1.试验用品
1)毒株：肠道病毒EV71和柯萨奇病毒CA16
2)细胞：Vero细胞
2.测试条件
1)温度：23-25℃
2)相对湿度:50-60％
3)试验时间：18小时
3.测试步骤
细胞毒性实验
参考标准ISO18184-2014及《消毒技术规范》2002版，裁剪测试样品备用，分别评价测试样品对细胞的毒性。
病毒杀灭实验
参考标准ISO18184-2014及《消毒技术规范》2002版，测试样品与病毒悬液作用18小时，回收样品检测病度，实验设置空白对照。
试验结果如下：
1.测试样对Vero细胞无毒性作用，细胞生长良好。
2.在本测试设置的实验条件下，测试样品与肠道病毒EV71和柯萨奇病毒CA16悬液作用18小时，测试样品对肠道病毒EV71和柯萨奇病毒CA16有一定的杀灭作用(表4)。
表4
Figure PCTCN2021097293-appb-000006
基于上述结果可知，本发明滤材对于病毒也有很好的杀灭效果，18小时的病毒杀灭率达到99％以上。
实施例6 本发明滤材与其他滤材的抗菌和抗病毒效果的比较
本发明滤材选用样品3进行实验。对照滤材分别采用可商购的用含铜丝滤材和含纳米银滤材。分别测试上述滤材对于大肠杆菌(Escherichia coli)和冠状病毒GX_P2V在5分钟和18小时的抗菌和抗病毒效果。测试方法参考前述实施例3-5。
试验结果如下：
表5
Figure PCTCN2021097293-appb-000007
基于上述结果可知，相比于含铜丝滤材和含纳米银滤材，本发明的滤材对于细菌和病毒均呈现优异的杀灭效果。而且，本发明的滤材不但可以实现快速的抗菌效果，而且此抗菌效果可以持续较长时间。
上述实验在18小时后并未结束。将样品3转移贴附在写字楼空气过滤器的出风口处，保持3个月，随后测定其杀菌的效果。平行对照使用未包含本发明铜涂覆层的普通PP材料作为滤材。测定方法参照实施例3。
表6
  大肠杆菌的杀菌率
处理时间 3个月之后
样品3 90.04％
普通PP材料 大量菌生长，基本失效
由此可知，本发明滤材可以实现长效性杀菌，杀菌效果可以保持至少3个月，3个月的杀菌效果依旧在90％以上，符合国家GB15979-2002标准中≥90％的要求。

Claims (10)

  1. 一种过滤材料，其特征在于所述过滤材料包括内部的过滤芯材和包覆在所述过滤芯材外层的包覆层，其中所述包覆层选自以下的一种或多种：铜、银、锌、金以及他们中一种或多种的合金。
  2. 如权利要求1的过滤材料，其特征在于所述包覆层均匀分布或非均匀分布在所述过滤芯材外层。
  3. 如权利要求1-2中任一项的过滤材料，其特征在于所述包覆层的厚度为0.001μm-500nm，优选0.001μm-300nm，优选0.001μm-100μm，优选0.1μm-1μm。
  4. 如权利要求1-3中任一项的过滤材料，其特征在于所述过滤芯材为滤丝形状。
  5. 如权利要求1-4中任一项的过滤材料，其特征在于所述滤丝的直径的范围为0.05μm-500μm，优选0.05μm-300μm，优选0.05μm-100μm，优选0.05μm-50μm，优选0.01μm-30μm，优选0.01μm-10μm，优选0.1μm-1μm。
  6. 如权利要求1-5中任一项的过滤材料，其特征在于所述过滤芯材选自包括以下的一种或多种：聚酯、聚酰胺、聚丙烯、聚苯硫醚、聚四氟乙烯、聚醚砜(PES)、醋酸纤维素(CA)、混合纤维素酯(MCE)、硝酸纤维素(NC)、聚偏二氟乙烯(PVDF)、尼龙(NV)、膨体聚四氟乙烯(EPTEF)、有玻璃纤维和陶瓷纤维。
  7. 如权利要求1-6中任一项的过滤材料在制备杀灭微生物，优选细菌和病毒的过滤制品中的用途。
  8. 一种过滤制品，其特征在于其包含如权利要求1-6中任一项所述的过滤材料。
  9. 如权利要求8的过滤制品，其特征在于其选自口罩滤芯、净化器滤芯、空调滤芯和通风口滤芯。
  10. 如权利要求8-9中任一项的过滤制品，其特征在于所述过滤制品可以进一步包括其它过滤材料，例如活性炭。
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CN104831528A (zh) * 2015-03-31 2015-08-12 嘉兴中科奥度新材料有限公司 高效空气粒子过滤无纺布复合离子镀纳米金属工艺及其制品
CN212818617U (zh) * 2020-06-01 2021-03-30 南京鼎卫空气净化有限公司 具有涂层的气体过滤结构和气体过滤制品

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Publication number Priority date Publication date Assignee Title
JPH04317728A (ja) * 1991-04-18 1992-11-09 Fuji Photo Film Co Ltd 複合濾過膜
CN103381316A (zh) * 2012-05-04 2013-11-06 东莞市导谷电子材料科技有限公司 一种具有杀菌抑菌作用的空气过滤网及制备方法
CN103935081A (zh) * 2014-02-26 2014-07-23 东莞市万丰纳米材料有限公司 一种具有无机杀菌抑菌作用的透气性材料及其制备方法
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