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CN112522861A - Application of composite nano particles of carbon and copper in melt-blown non-woven material - Google Patents

Application of composite nano particles of carbon and copper in melt-blown non-woven material Download PDF

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Publication number
CN112522861A
CN112522861A CN202011435076.9A CN202011435076A CN112522861A CN 112522861 A CN112522861 A CN 112522861A CN 202011435076 A CN202011435076 A CN 202011435076A CN 112522861 A CN112522861 A CN 112522861A
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carbon
copper
melt
composite
coppware
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连崑
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Suzhou Guanjie Nano Material Technology Co Ltd
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Suzhou Guanjie Nano Material Technology Co Ltd
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Priority to PCT/CN2020/135843 priority Critical patent/WO2022077753A1/en
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    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/56Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • D01F1/103Agents inhibiting growth of microorganisms

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Respiratory Apparatuses And Protective Means (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Filtering Materials (AREA)

Abstract

The invention relates to application of composite nano particles of carbon and copper as an anti-virus additive and/or an electret material of a melt-blown non-woven material, wherein the composite nano particles of the carbon and the copper comprise a Coppware R copper carbon R composite material which comprises a carbon shell with a porous structure and copper nano particles wrapped in the carbon shell. The invention discloses an antiviral effect of composite nano particles of carbon and copper, and the composite nano particles can play an electret effect when being used in melt-blown non-woven materials.

Description

Application of composite nano particles of carbon and copper in melt-blown non-woven material
Technical Field
The invention relates to the technical field of melt-blown non-woven materials, in particular to application of composite nano particles of carbon and copper in melt-blown non-woven materials.
Background
The Coppware R copper carbon R composite material is a carbon and copper composite nanoparticle prepared by taking plant fiber as a template and metal copper ions as a raw material through a heating carbonization reduction method. The composite nanoparticles of carbon and copper have many different and superior effects compared to the existing copper nanoparticle materials on the market.
CN102499260 and CN108653240 disclose the application of the above composite nanoparticles of carbon and copper in antibacterial aspect and in preparing antibacterial agent, antistaling agent, medicine for promoting glycolipid metabolism, weight-reducing medicine, food additive or animal feed, respectively. It is not known whether the material has other uses.
At present, a large amount of melt-blown non-woven materials are required to be used in the production process of the mask, and the existing melt-blown non-woven materials do not have the antiviral effect. Meanwhile, since the mask needs to have a filtering effect, an electret is a dielectric material having a standard permanent charge and is generally added. The electret material is formed by adding electric charges into fibers of the melt-blown non-woven fabric, and the electret material has the obvious effects of reducing the filtering resistance of the melt-blown non-woven fabric and improving the filtering efficiency. If the electret material is not added into the melt-blown nonwoven material, the filtration efficiency of the melt-blown nonwoven material cannot be stably up to more than 95 percent. In the beginning of the 21 st century, products using inorganic powder such as tourmaline, silicon dioxide and zirconium phosphate as an electret master batch charge enhancer and the technology thereof are rapidly developed, but the problems of limited addition amount of the inorganic powder, strict requirement on powder granularity, easy blockage of a spinneret plate, short cleaning period of the spinneret plate and the like exist. And then, the technology of modifying the inorganic powder by organic components such as stearic acid, vinyl bis stearamide and the like is developed rapidly, so that the functional efficiency of the inorganic powder is obviously improved, and the production process of the melt-blown non-woven fabric is also effectively improved. Therefore, it is necessary to develop more and more materials that can be used as electrets.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide application of composite nano particles of carbon and copper in melt-blown non-woven materials.
A first object of the present invention is to disclose the use of composite nanoparticles of carbon and copper as an antiviral additive and/or electret material for meltblown nonwoven materials, the composite nanoparticles of carbon and copper comprising a Coppware R copper carbon R composite comprising a carbon shell having a porous structure and copper nanoparticles encased in the carbon shell.
Further, in the Coppware R copper-carbon R composite material, the mass ratio of the copper element to the carbon element is about 1: 3-3.5.
Further, the carbon shell is porous carbon black.
Further, the antiviral additive is used for resisting one or more of influenza A virus (H3N2), hepatitis B virus (HBV-Ad38) and enterovirus type 68 (EV-D68).
Further, when the composite nano particles are used as an antiviral additive, the composite nano particles of carbon and copper account for 0.5 to 10 percent of the mass fraction of the melt-blown non-woven material. Preferably, the composite nanoparticles of carbon and copper comprise 1-5% by mass of the meltblown nonwoven material.
Further, when the composite nano-particles are used as the electret material, the composite nano-particles of carbon and copper account for 0.5 to 10 percent of the mass fraction of the melt-blown non-woven material. Preferably, the composite nanoparticles of carbon and copper comprise 1-2% by mass of the meltblown nonwoven material.
Further, the meltblown nonwoven material includes meltblown fibers having a diameter of 0.05 microns to 200 microns. Preferably, the meltblown fibers have a diameter of 0.05 to 5 microns.
Further, the material of the melt-blown non-woven material is thermoplastic polymer. Thermoplastic polymers can be made into nonwoven fibers using a melt-blown process. Preferably, the thermoplastic polymer is PP (polypropylene), PP-R (random copolymer polypropylene), CA (cellulose acetate), CE (general purpose cellulose plastic), PA (polyamide), PE (polyethylene), UHMWPE (ultra high molecular weight polyethylene), PAN (polyacrylonitrile), PVAL (polyvinyl alcohol), TPU (thermoplastic polyurethane), silicone plastic, EPM (ethylene/propylene copolymer ethylene propylene resin), EPS (expandable polystyrene expanded polystyrene), EVA (ethylene/vinyl acetate copolymer), HDPE (high density polyethylene low pressure polyethylene), LDPE (low density polyethylene high pressure polyethylene), LLDPE (linear low density polyethylene linear high pressure polyethylene), MF (melamine-formaldehyde resin melamine plastic), PAI (polyamide-imide), PBT (polybutylene terephthalate polyester), PC (polycarbonate), PET (polyethylene terephthalate polyester (linear) resin), PUR (polyurethane urethane), PU (polyurethane urethane), PVC polyvinyl chloride), and the like.
Further, the raw materials for making meltblown nonwoven materials include thermoplastic polymers, hydrogels, coating materials, textiles, and solvents. The solvent comprises water or other polar or non-polar solution capable of dissolving the above raw materials.
Further, the porosity of the meltblown nonwoven material is between 0.5% and 90%. Preferably, the porosity of the meltblown nonwoven material is between 50 and 80%.
A second object of the invention is to claim a meltblown nonwoven material comprising composite nanoparticles of carbon and copper, the composite nanoparticles of carbon and copper comprising a Coppware R copper carbon R composite comprising a carbon shell having a porous structure and copper nanoparticles encased in the carbon shell.
The Coppware R copper carbon R composite material is added into the melt-blown non-woven material, so that the effects of resisting virus and bacteria simultaneously can be achieved, and the effect of serving as an electret can be achieved. The Coppware R copper carbon R composite may be incorporated into the interior of the meltblown nonwoven or coated onto the surface of the meltblown nonwoven.
Further, when the Coppware R copper carbon R composite is added to the meltblown nonwoven material as an electret, no other substances than the Coppware R copper carbon R composite are added to the meltblown nonwoven material that can be used as an electret material.
A third object of the present invention is to claim a mask comprising the meltblown nonwoven material described above.
Masks containing the meltblown nonwoven material described above have an antiviral effect and may be free of traditional electret materials other than Coppware R copper carbon R composites.
Further, in the invention, the Coppware R copper-CARBON R composite material is prepared by taking plant fibers as templates AND metallic copper ions as raw materials in a heating carbonization reduction method in the application date OF 2007.2.8 days, the international publication number OF WO/2007/095454 AND the international application number OF PCT/US2007/061862, the invention name OF "CARBON-ENCASED METAL NANOPROPERICLES AND SPONGES, METHODS OF SYNTHESIS, AND METHODS OF USE" (CARBON-coated metal NANOPARTICLES AND SPONGES AND the preparation method AND the USE method thereof), wherein the preparation method is also the method disclosed in the patent. In the carbon and copper composite nano particle, nano copper is uniformly embedded in porous carbon black, and the surface of the nano copper is provided with a balance system of copper and cuprous oxide, so that the nano copper composite nano particle has a unique renewable function. The additive has low copper ion leaching rate, low biological toxicity and less environmental pollution even after being metabolized and discharged out of the body.
By the scheme, the invention at least has the following advantages:
the invention discloses an antiviral effect of composite nano particles of carbon and copper, and the composite nano particles can play an electret effect when being used in melt-blown non-woven materials. The novel melt-blown fabric has a virus killing effect of up to 100% on different viruses, and after long-time exposed storage, the filtering effect has no obvious change, so that the novel melt-blown fabric meets the requirement of N95 melt-blown fabric, and a new direction is provided for developing new melt-blown fabrics and masks.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a preferred embodiment of the present invention and is described in detail below.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the following examples of the present invention, the Coppware R copper carbon R composite material used comprises a carbon shell having a plurality of pores and copper nanoparticles wrapped in the carbon shell, and the mass ratio of copper element to carbon element is 1: 3. Specifically, the material is prepared by taking plant fibers as templates AND metal copper ions as raw materials in a heating carbonization reduction method in the invention with the application date OF 2007.2.8, the international publication number OF WO/2007/095454, the international application number OF PCT/US2007/061862, the invention name OF "CARBON-ENCASED METAL NANOPROPORTICLES AND SPONGES, METHODS OF SYNTHESIS, AND METHODS OF USE" (CARBON-coated metal NANOPARTICLES AND SPONGES AND a preparation method AND a USE method thereof), wherein the preparation method is also the method disclosed in the patent.
Example 1
The antivirus performance of the Coppware R copper-carbon R composite material, the cloth containing the material and the mask sample is tested, and meanwhile, 100% cotton fabric or an untreated sample to be tested, which is specified by ISO105-F02, is selected as a control sample.
The HA inhibition method is used for testing the antiviral property of different samples on influenza A virus (H3N2), the HBsAg/HBeAg detection method is used for testing the antiviral property of different samples on hepatitis B virus (HBV-Ad38), and the TCID50 method is used for testing the antiviral property of different samples on enterovirus type 68 (EV-D68). The test cell lines were:
MDCK cells (suitable for influenza virus detection)), HepG2-hNTCP cells (suitable for hepatitis b virus detection), RD cells (human rhabdomyoma cells, suitable for enterovirus detection)).
For the Coppware R copper carbon R composite material, a sample to be detected with corresponding mass is directly weighed according to the table 1 and is placed into a screw-cap bottle for standby. For the cloth containing the Coppware R copper carbon R composite material and the mask sample or the control group pure cotton cloth, respectively weighing corresponding mass of samples to be detected, cutting the samples into sample blocks with the size of 20 multiplied by 20mm, and placing the sample blocks into a screw cap bottle for later use. Wherein in the mask and the melt-blown cloth containing the Coppware R copper-carbon R composite material, the Coppware R copper-carbon R composite material accounts for 1-2% of the mass fraction of the melt-blown non-woven material.
Table 1 different test set-ups
Figure BDA0002828257260000041
The samples are sent to the national center for research on infectious disease diagnostic reagent and vaccine engineering technology of Xiamen university for antiviral test, and the test results show that the B2 sample has 100 percent, 94 percent and 99 percent of virucidal rate on influenza A virus (H3N2), hepatitis B virus (HBV-Ad38) and enterovirus 68 (EV-D68) respectively.
The above samples were sent to the center for microbiological analysis and detection in Guangdong province, and antibacterial and antiviral tests were carried out according to GB/T20944.3-2008 oscillation method and ISO18184:2014(E), respectively, and the results are shown in tables 2-3:
TABLE 2 results of antibacterial tests
Figure BDA0002828257260000042
Figure BDA0002828257260000051
TABLE 3 results of antiviral tests
Figure BDA0002828257260000052
Figure BDA0002828257260000061
A recent study at hong kong university showed that on day 7, the outer layer of the common surgical mask may still have detectable infectious virus. The results show that the melt-blown fabric compounded with the Coppware R copper-carbon R composite material has excellent antiviral effect.
Example 2
Firstly, preparing melt-blown cloth compounded with Coppware R copper-carbon R composite material, which comprises the following steps:
preparing PP master batch containing 20 wt% of COPPPWARE, adding the PP master batch (2.5-50%) in relative proportion according to the content (0.5-10%) of the COPPPware R copper-carbon R composite material required by different melt-blown fabrics, uniformly premixing the PP master batch with PP slices, and producing according to a conventional melt-blown fabric production process. In the preparation process of the melt-blown fabric compounded with the Coppware R copper carbon R composite material, other conventional electret master batch materials are not added.
In the melt-blown fabric preparation process of the Coppware R copper-carbon R composite material, the Coppware R copper-carbon R composite material can account for 0.5-10% of the mass fraction of the melt-blown fabric, and can be specifically adjusted according to requirements. The filter effect of the melt-blown cloth prepared by compounding the Coppware R copper-carbon R composite material is tested according to the specification of GB/T32610-2016 appendix A, the test environment temperature is (25 +/-5) DEG C, and the relative humidity is (30 +/-10)%. And (3) connecting the melt-blown fabric to a detection device in an airtight manner by using a proper clamp, and recording the filtration efficiency of the sample after the detection is started, wherein the sampling frequency is more than or equal to 1 time/min. The test should be continued until the particles on the meltblown fabric are loaded to 30 mg.
For comparison, a conventional PP meltblown was used as a control. The test was carried out in the same manner. If the electret master batch is not added to the common melt-blown fabric, the filtration efficiency of the common melt-blown fabric cannot stably reach more than 95 percent.
After the Coppware R copper carbon R composite material is added into the melt-blown cloth (the addition amount is 0.5-10%), the filtering efficiency can be obviously improved, and the effect of replacing the existing electret master batch is realized. Tables 4-5 are statistical tables of the filtration efficiency before and after 72 hours of storage of meltblown fabric with 1 wt% Coppware R copper carbon R composite material and without conventional electret masterbatch, and the results show that the filtration efficiency does not change significantly after more than 72 hours of naked storage, and meets the requirements of N95 meltblown.
TABLE 4 statistical table of filtering effect before and after 72h storage with gas flow of 32.4L/min
Figure BDA0002828257260000062
Figure BDA0002828257260000071
TABLE 5 statistical table of filtering effect before and after 72h storage at 85.0L/min gas flow
0h 72h
Resistance force 86.5Pa 86.7Pa
0.3μm The filtration efficiency is 96.3654% The filtration efficiency is 94.0725%
0.5μm The filtration efficiency is 97.3847% The filtration efficiency is 95.2914%
1.0μm The filtration efficiency is 99.7003% The filtration efficiency is 99.2508%
3.0μm The filtration efficiency is 100.0000% The filtration efficiency is 99.4480%
5.0μm The filtration efficiency is 100.0000% The filtration efficiency is 100.0000%
10.0μm The filtration efficiency is 100.0000% The filtration efficiency is 100.0000%
The efficient filtration efficiency of meltblown fabrics depends on their inherent electrostatic holding capacity. The filtering efficiency of the mask is improved, the key point is electrostatic storage of the melt-blown non-woven fabric, under the current mask circulation speed, the attenuation of static electricity is not enough (for example, half a month to a user after delivery), while the valid period of normal medical masks is 6 months, while the valid period of some masks in Japan is three years.
The melt-blown nonwoven electret is very sensitive to the ambient humidity. The surface potential of the sample of the positive corona charging sample and the sample of the negative corona charging sample are respectively reduced to 28 percent and 36 percent of the initial value after the common PP melt-blown non-woven fabric is stored for 7 days under the condition of normal temperature and high humidity (the relative humidity is more than 95 percent). The reason is that the melt-blown non-woven fabric is provided with an open structure, the specific surface area of the melt-blown non-woven fabric is larger, and the melt-blown non-woven fabric has a larger contact surface with the surrounding environment, so that the melt-blown non-woven fabric is more sensitive to water vapor, corrosive gas, oppositely charged particles and the like in the environment, meanwhile, a corona charging system can only generate ion charges with low beam energy, and most of the charges injected in the charging process are deposited on the near-surface layer of the surface layer fibers of the fabric. When samples are stored or operated in high humidity environments, a large loss of charge is caused by the compensatory effect of polar groups in water molecules, foreign ions in the atmosphere, etc. on the high concentration of surface charges on the fibers. The meltblown fabric compounded with the Coppware R copper carbon R composite material can react with polar groups in water molecules and foreign ions in the atmosphere due to the equilibrium reaction of metal copper and monovalent copper ions of the Coppware material and the special physical structure of the nano copper core/graphene shell, so that the loss speed and the quantity of charges on the surface of the meltblown fabric are remarkably reduced, and the filtration efficiency and the storage time of the meltblown fabric are improved.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (10)

1. Use of composite nanoparticles of carbon and copper as an anti-viral additive and/or an electret material for meltblown nonwoven materials, the composite nanoparticles of carbon and copper comprising a Coppware R copper carbon R composite comprising a carbon shell having a porous structure and copper nanoparticles entrapped in the carbon shell.
2. Use according to claim 1, characterized in that: in the Coppware R copper-carbon R composite material, the mass ratio of the copper element to the carbon element is about 1: 3-3.5.
3. Use according to claim 1, characterized in that: the antiviral additive is used for resisting one or more of influenza A virus, hepatitis B virus and enterovirus 68.
4. Use according to claim 1, characterized in that: when the composite nano particles are used as an antiviral additive, the composite nano particles of the carbon and the copper account for 0.5 to 10 percent of the mass fraction of the melt-blown non-woven material.
5. Use according to claim 1, characterized in that: when the composite nano-particles are used as an electret material, the composite nano-particles of carbon and copper account for 0.5-10% of the mass fraction of the melt-blown non-woven material.
6. Use according to any one of claims 1 to 5, characterized in that: the meltblown nonwoven material includes meltblown fibers having a diameter of 0.05 microns to 200 microns.
7. Use according to any one of claims 1 to 5, characterized in that: the material of the melt-blown non-woven material comprises thermoplastic polymer.
8. Use according to any one of claims 1 to 5, characterized in that: the porosity of the melt-blown nonwoven material is 0.5% -90%.
9. A meltblown nonwoven material characterized by: composite nanoparticles comprising carbon and copper, the composite nanoparticles comprising a Coppware R copper carbon R composite comprising a carbon shell having a porous structure and copper nanoparticles encased in the carbon shell.
10. A mask, characterized in that: comprising the meltblown nonwoven material of claim 9.
CN202011435076.9A 2020-10-12 2020-12-10 Application of composite nano particles of carbon and copper in melt-blown non-woven material Pending CN112522861A (en)

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CN115198391A (en) * 2022-05-25 2022-10-18 苏州冠洁纳米材料科技有限公司 Composite fiber material with slow release function and application thereof

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CN115198391A (en) * 2022-05-25 2022-10-18 苏州冠洁纳米材料科技有限公司 Composite fiber material with slow release function and application thereof

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Application publication date: 20210319