CN113684611A - Antibacterial and mildewproof melt-blown non-woven fabric - Google Patents
Antibacterial and mildewproof melt-blown non-woven fabric Download PDFInfo
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- CN113684611A CN113684611A CN202111163561.XA CN202111163561A CN113684611A CN 113684611 A CN113684611 A CN 113684611A CN 202111163561 A CN202111163561 A CN 202111163561A CN 113684611 A CN113684611 A CN 113684611A
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- melt
- antibacterial
- cuprous oxide
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 250
- 239000004750 melt-blown nonwoven Substances 0.000 title claims abstract description 118
- 239000004744 fabric Substances 0.000 title claims abstract description 117
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 198
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 198
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 197
- 239000004743 Polypropylene Substances 0.000 claims abstract description 194
- 229920001155 polypropylene Polymers 0.000 claims abstract description 194
- -1 polypropylene Polymers 0.000 claims abstract description 181
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 151
- 238000002156 mixing Methods 0.000 claims abstract description 74
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- 238000002360 preparation method Methods 0.000 claims abstract description 39
- 238000009987 spinning Methods 0.000 claims abstract description 24
- 238000001125 extrusion Methods 0.000 claims abstract description 12
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- 239000000376 reactant Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 150000001879 copper Chemical class 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 11
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 6
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 6
- QOKYJGZIKILTCY-UHFFFAOYSA-J hydrogen phosphate;zirconium(4+) Chemical compound [Zr+4].OP([O-])([O-])=O.OP([O-])([O-])=O QOKYJGZIKILTCY-UHFFFAOYSA-J 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 15
- 239000004745 nonwoven fabric Substances 0.000 abstract description 15
- 230000003115 biocidal effect Effects 0.000 abstract description 9
- 239000003242 anti bacterial agent Substances 0.000 abstract description 7
- 238000002844 melting Methods 0.000 description 43
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- 239000011449 brick Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 231100000135 cytotoxicity Toxicity 0.000 description 3
- 230000003013 cytotoxicity Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- VBQMPXNFLQSHMH-UHFFFAOYSA-N Arlatin Chemical compound C1CC(C)(O)C2(O)CC=C(C)C2C2OC(=O)C(C)C21 VBQMPXNFLQSHMH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 241000228245 Aspergillus niger Species 0.000 description 1
- 241000079253 Byssochlamys spectabilis Species 0.000 description 1
- 241001515917 Chaetomium globosum Species 0.000 description 1
- 241001136494 Talaromyces funiculosus Species 0.000 description 1
- 241000223262 Trichoderma longibrachiatum Species 0.000 description 1
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- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 231100000263 cytotoxicity test Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 239000003623 enhancer Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 231100001083 no cytotoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Images
Classifications
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING 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
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-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
- D04H1/54—Non-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
- D04H1/56—Non-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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING 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
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-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
- D04H1/54—Non-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
- D04H1/542—Adhesive fibres
- D04H1/544—Olefin series
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The application belongs to the technical field of the non-woven fabrics, especially, relate to an antibiotic mould proof melt-blown non-woven fabrics. The application provides antibiotic mould proof melt-blown non-woven fabrics includes: mixing the nano cuprous oxide antibacterial polypropylene master batch with melt-blown polypropylene, and performing melt filtration, air flow traction, spinning, web formation, coiling and finished product after melt extrusion to obtain the antibacterial and mildewproof melt-blown non-woven fabric; the preparation method of the nano cuprous oxide antibacterial polypropylene master batch comprises the following steps: mixing soluble copper salt and alkali liquor for reaction, and carrying out solid-liquid separation to obtain a solid reactant; mixing the solid reactant with a reducing agent for reaction, and carrying out solid-liquid separation and drying to obtain nano cuprous oxide; mixing nano cuprous oxide, high-temperature-resistant filler and master batch polypropylene, then performing melt extrusion, and then granulating to obtain the nano cuprous oxide antibacterial polypropylene master batch. The application provides an antibiotic mould proof melt-blown non-woven fabrics effectively solves current antibiotic non-woven fabrics and strains the technical problem that the effect is low and biological safety is low.
Description
Technical Field
The application belongs to the technical field of the non-woven fabrics, especially, relate to an antibiotic mould proof melt-blown non-woven fabrics.
Background
The production process of the melt-blown non-woven fabric comprises the steps of mixing, storing a hopper, extruding and melting by a screw at 240 ℃, conveying a high-pressure melt, filtering, air-flow traction, spinning, forming a net, coiling and obtaining a finished product. The color of the finished product is pure white, and the finished product is a key material for manufacturing the middle layer of the mask. The quality standards of the evaluated mask comprise filtering effect, breaking strength, chromatic aberration and the like, wherein the filtering effect generally reaches more than 95%, the breaking strength of the non-woven fabric is not less than 10N in the transverse direction and not less than 15N in the longitudinal direction, and the chromatic aberration level of the same batch is 4-5.
The antibacterial master batch refers to an antibacterial resin concentrate formed by mechanically mixing an antibacterial powder auxiliary agent with thermoplastic resin, uniformly distributing the antibacterial powder in molten resin at a certain high temperature, and cooling and hardening. When the melt-blown non-woven fabric is manufactured, the antibacterial effect of the melt-blown non-woven fabric can be realized only by adding the antibacterial master batch into a melt-blown raw material according to a certain proportion.
In the market at the present stage, the cuprous oxide antibacterial melt-blown non-woven fabric is mainly produced by adding a micron-sized cuprous oxide antibacterial agent into polypropylene particles at a material mixing stage, stirring and mixing uniformly, and because the micron-sized or submicron-sized cuprous oxide has weak antibacterial activity, the addition amount of antibacterial powder is large, so that a plurality of adverse results are brought, and firstly, the appearance color of the traditional pure white non-woven fabric is changed into brick red apparently; secondly, the cuprous oxide has potential biological safety problem due to large addition amount, so that the safety risk of a user is increased; thirdly, the filtering effect of the non-woven fabric is reduced due to the addition of the micron-sized cuprous oxide, and the quality of the original non-woven fabric is influenced. Therefore, there is a need for an antibacterial meltblown nonwoven fabric which has good biosafety, good bacteriostatic effect and no odor without changing the quality of meltblown nonwoven fabric, including appearance color, filtration effect, tensile toughness and the like.
Disclosure of Invention
In view of this, the application provides an antibiotic mould proof melt-blown non-woven fabrics, effectively solves the ubiquitous technical problem that strains the effect and the biological safety is low of current antibiotic non-woven fabrics.
The application provides an antibacterial and mildewproof melt-blown non-woven fabric which is prepared by the following preparation method:
mixing the nano cuprous oxide antibacterial polypropylene master batch with melt-blown polypropylene, and performing melt filtration, air flow traction, spinning, web formation, coiling and finished product after melt extrusion to obtain the antibacterial and mildewproof melt-blown non-woven fabric;
the preparation method of the nano cuprous oxide antibacterial polypropylene master batch comprises the following steps:
and 2, mechanically mixing the nano cuprous oxide, the high-temperature-resistant filler and the master batch polypropylene, performing melt extrusion, and then granulating to obtain the nano cuprous oxide antibacterial polypropylene master batch.
Specifically, the melt-blown polypropylene used for preparing the antibacterial and mildewproof melt-blown non-woven fabric and the masterbatch polypropylene in the step 2 are conventional polypropylenes, but the molecular weights of the polypropylene and the masterbatch polypropylene are not consistent, the masterbatch polypropylene for preparing the nano cuprous oxide antibacterial polypropylene masterbatch is a polypropylene with a high melt index and the melt-blown polypropylene for preparing the antibacterial and mildewproof melt-blown non-woven fabric is a polypropylene with a low melt index and a low molecular weight.
In another embodiment, the method comprises the following steps of calculating according to mass percentage
0.64 to 4 percent of nano cuprous oxide antibacterial polypropylene master batch;
96-99.36% of melt-blown polypropylene.
Specifically, the preparation method of the antibacterial and mildewproof melt-blown non-woven fabric comprises the following steps:
mixing the following raw materials in percentage by mass:
0.64-4% of nano cuprous oxide antibacterial polypropylene master batch and 96-99.36% of melt-blown polypropylene, and the antibacterial and mildewproof melt-blown non-woven fabric is obtained by mixing, storing a hopper, extruding and melting by a high-temperature screw, conveying high-pressure melt, filtering, air-flow drawing, spinning, forming a net, coiling and forming a finished product, and is white, the filtering efficiency is higher than 99%, and no peculiar smell is generated.
In another embodiment, in step 1, the soluble copper salt is selected from copper chloride or/and copper acetate; the alkali liquor is selected from sodium hydroxide solution or/and potassium hydroxide solution.
In another embodiment, the reducing agent is selected from sodium borohydride or/and ascorbic acid.
Specifically, the soluble copper salt is copper chloride; the alkali liquor is sodium hydroxide; the reducing agent is ascorbic acid or sodium borohydride.
In another embodiment, in the step 1, the molar mass ratio of the soluble copper salt to the alkali liquor is 1 (1.5-3.5); the molar mass ratio of the solid reactant to the reducing agent is 1 (0.01-1).
Specifically, in the step 1, the molar mass ratio of copper chloride to sodium hydroxide is 1: 2; the molar mass ratio of the solid reactant to the sodium borohydride or the ascorbic acid is 5: 1.
Specifically, the preparation of nano cuprous oxide (20-120 nm): feeding a copper chloride solution and a sodium hydroxide solution according to a molar mass ratio of 1:2, reacting at 10-30 ℃, stirring for 0.5-1 hour, and filtering to obtain blue filter residue. Feeding the blue filter residue and sodium borohydride or ascorbic acid solution according to a molar mass ratio of 5:1, reacting at 10-30 ℃ for 12-24 hours, performing suction filtration to obtain yellow-green filter residue, vacuum-drying at 60-90 ℃ for 6 hours, and collecting to obtain the nano cuprous oxide.
Further, the appearance of the nano cuprous oxide is yellow green, the particle size is 20-120nm, and preferably, the particle size of the nano cuprous oxide is 60-120 nm.
In another embodiment, in step 2, the high temperature resistant filler is selected from one or more of natural zeolite, artificial zeolite, kaolin, talcum powder, titanium dioxide, barium sulfate powder, calcium carbonate powder and zirconium hydrogen phosphate.
In another embodiment, in step 2, the step of,
calculated according to mass percent, comprising
0.5 to 2.5 percent of nano cuprous oxide;
4.5 to 47.5 percent of high-temperature resistant filler;
50-95% of master batch polypropylene.
In another embodiment, in the step 2, the nano cuprous oxide, the high temperature resistant filler and the thermoplastic resin are mixed at normal temperature, and the mixture is stirred in a high-speed stirrer at a speed of 1000-2000 r/min for 20-30 min.
In another embodiment, in the step 2, the mixture is transferred to a double-screw extruder, and is subjected to high-temperature melting, cooling, cutting and granulation to obtain the yellowish green nano cuprous oxide antibacterial polypropylene master batch.
Specifically, the melting temperature in step 2 is 180-240 ℃.
Specifically, the raw materials are mixed according to the following mass percentage: 0.5-2.5% of nano cuprous oxide (20-120nm), 4.5-47.5% of high-temperature resistant filler and 50-95% of master batch polypropylene, stirring the mixture for 20-30 min at the normal temperature in a high-speed stirrer at 1000-2000 r/min to obtain a mixture, transferring the mixture to a double-screw extruder, and carrying out melting, cooling, cutting and granulating at 180 ℃ to obtain the nano cuprous oxide antibacterial polypropylene master batch which is yellow-green.
Firstly, the application provides novel nano cuprous oxide (yellow green, 20-120nm) with the highest antibacterial and mildewproof efficiency, and the antibacterial rates of escherichia coli and staphylococcus aureus can reach 99.9% by 16ppm respectively; secondly, the application utilizes the nano cuprous oxide as one of the three components to prepare the yellow-green nano cuprous oxide antibacterial polypropylene master batch, and the process is simplified; in addition, according to the application, the nano cuprous oxide antibacterial polypropylene master batch with extremely low addition amount is mixed with the melt-blown polypropylene and then melt-blown to prepare the antibacterial melt-blown non-woven fabric which is white, has the filtering effect of more than 99 percent, has the antibacterial effect of more than 99 percent and is mildew-proof 0 grade, the content of the nano cuprous oxide antibacterial polypropylene master batch of the antibacterial melt-blown non-woven fabric is as low as 6.4 per mill (w/w), the content of the nano cuprous oxide in the antibacterial mildew-proof melt-blown non-woven fabric is as low as 32ppm, and the extremely low addition amount realizes that the antibacterial mildew-proof melt-blown non-woven fabric is completely nontoxic and has good biological safety.
Compared with the prior art, the method has the following advantages:
(1) the synthesized nano cuprous oxide (yellow green, 20-120nm) is most efficient, and the antibacterial rates of escherichia coli and staphylococcus aureus can reach 99.9% respectively only by 16ppm of addition amount;
(2) the nano cuprous oxide antibacterial polypropylene master batch synthesized based on nano cuprous oxide (yellow green, 20-120nm) has simple components, only needs the nano cuprous oxide, the high-temperature-resistant filler and the master batch polypropylene, and does not need to add antioxidant, lubricant, charge enhancer, polybutene, initiator, dispersant and other oxide alloy components;
(3) according to the application, the minimum amount of the nano cuprous oxide antibacterial polypropylene master batch is added to obtain the antibacterial mildew-proof melt-blown non-woven fabric which is white in appearance, more than 99% in filter effect, more than 99% in antibacterial property and 0-level in mildew resistance, the content of the antibacterial polypropylene master batch of the antibacterial mildew-proof melt-blown non-woven fabric is as low as 6.4 per thousand (w/w), the content of the nano cuprous oxide in the antibacterial mildew-proof melt-blown non-woven fabric is as low as 32ppm, and a cytotoxicity experiment shows that the antibacterial melt-blown non-woven fabric is completely nontoxic due to the fact that the extremely low content of the nano cuprous oxide of 32ppm is achieved, and the antibacterial mildew-blown non-woven fabric has good biological safety.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is an SEM image of nano cuprous oxide with particle size of 20-120nm provided in example 1 of the present application;
fig. 2 is an XRD pattern of nano-cuprous oxide nanoparticles provided in examples 1 and 15 of the present application;
fig. 3 is an appearance diagram of the nano cuprous oxide antibacterial polypropylene masterbatch provided in embodiment 1 of the present application;
fig. 4 is an appearance diagram of the antibacterial melt-blown non-woven fabric based on the nano cuprous oxide antibacterial polypropylene masterbatch M1 provided in example 1 of the present application;
FIG. 5 is an SEM image of nano cuprous oxide with particle size of 60-120nm provided by example 15 of the present application.
Detailed Description
The application provides an antibiotic mould proof melts and spouts non-woven fabrics for solve among the prior art antibiotic non-woven fabrics and strain the technical defect that the effect is low and biological security is low.
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The raw materials and reagents used in the following examples are commercially available or self-made.
The reagents or raw materials used in the following examples are commercially available or self-made, with brick-red micron-sized cuprous oxide (1-5 μm) available from Shanghai Arlatin Biotech, Inc.
The melt index of the master batch polypropylene PP used in the following examples is 30g/10 min; the melt index of the melt blown polypropylene was 1500g/10 min.
Example 1
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
step one, preparing nano cuprous oxide (20-120 nm): feeding a copper chloride solution and a sodium hydroxide solution according to a molar mass ratio of 1:2, reacting at 25 ℃, stirring for 1 hour, and filtering to obtain blue filter residue. Feeding the blue filter residue and a sodium borohydride solution according to a molar mass ratio of 5:1, carrying out suction filtration to obtain yellow-green filter residue, carrying out vacuum drying at 90 ℃ for 6 hours, and collecting nano cuprous oxide which is yellow-green, wherein the reaction temperature is 25 ℃, the stirring time is 12 hours.
Step two, preparing the nano cuprous oxide antibacterial polypropylene master batch M1: mixing the following raw materials in percentage by mass: 0.5% of nano cuprous oxide (20-120nm), 4.5% of zeolite powder and 95% of master batch polypropylene (PP), stirring for 15min at normal temperature at 1500r/min in a high-speed stirrer to obtain a mixture, transferring the mixture to a double-screw extruder, and carrying out melting, cooling, cutting and granulation at 180 ℃ to obtain nano cuprous oxide antibacterial polypropylene master batch M1, wherein the nano cuprous oxide antibacterial polypropylene master batch M1 is yellow-green.
Step three, preparing the antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: 10.64 percent of nano cuprous oxide antibacterial polypropylene master batch and 99.36 percent of melt-blown polypropylene are subjected to mixing, storage hopper, 240 ℃ screw extrusion melting, high-pressure melt conveying, filtering, air flow traction, spinning, net forming, coiling and finished product forming to obtain the antibacterial melt-blown non-woven fabric which is white.
Wherein, SEM picture of nanometer cuprous oxide (20-120nm) is shown in figure 1, XRD of nanometer cuprous oxide (20-120nm) is shown in figure 2# 1, appearance of nanometer cuprous oxide antibacterial polypropylene mother particle M1 is shown in figure 3, and appearance of antibacterial melt-blown non-woven fabric based on nanometer cuprous oxide antibacterial polypropylene mother particle M1 is shown in figure 4.
Example 2
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
step one, the nano cuprous oxide is prepared in the same way as the step one of the embodiment 1.
Step two, preparing the nano cuprous oxide antibacterial polypropylene master batch M2: mixing the following raw materials in percentage by mass: 0.5% of nano cuprous oxide (20-120nm), 4.5% of talcum powder and 95% of master batch polypropylene, stirring for 15min at normal temperature in a high-speed stirrer at 1500r/min to obtain a mixture, transferring the mixture to a double-screw extruder, and performing melting, cooling, cutting and granulation at 180 ℃ to obtain nano cuprous oxide antibacterial polypropylene master batch M2, wherein the nano cuprous oxide antibacterial polypropylene master batch M2 is yellow-green.
Step three, preparing the antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: 20.64 percent of nano cuprous oxide antibacterial polypropylene master batch and 99.36 percent of melt-blown polypropylene, and the antibacterial melt-blown non-woven fabric is obtained by mixing, storing a hopper, extruding and melting by a screw at 240 ℃, conveying by high-pressure melt, filtering, air-flow drawing, spinning, forming a net, coiling and forming a finished product, and is white.
Example 3
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
step one, the nano cuprous oxide is prepared in the same way as the step one of the embodiment 1.
Step two, preparing the nano cuprous oxide antibacterial polypropylene master batch M3: mixing the following raw materials in percentage by mass: 0.5% of nano cuprous oxide (20-120nm), 4.5% of kaolin and 95% of master batch polypropylene (PP), stirring for 15min at the normal temperature at 1500r/min in a high-speed stirrer to obtain a mixture, transferring the mixture to a double-screw extruder, and carrying out melting, cooling, cutting and granulation at 180 ℃ to obtain nano cuprous oxide antibacterial polypropylene master batch M3, wherein the nano cuprous oxide antibacterial polypropylene master batch M3 is yellow-green.
Step three, preparing the antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: 30.64% of nano cuprous oxide antibacterial polypropylene master batch and 99.36% of melt-blown polypropylene, and the antibacterial melt-blown non-woven fabric is obtained by mixing, storing a hopper, extruding and melting by a screw at 240 ℃, conveying by high-pressure melt, filtering, air-flow drawing, spinning, forming a net, coiling and forming a finished product, wherein the antibacterial melt-blown non-woven fabric is white.
Example 4
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
step one, the nano cuprous oxide is prepared in the same way as the step one of the embodiment 1.
Step two, preparing the nano cuprous oxide antibacterial polypropylene master batch M4, namely mixing the following raw materials in percentage by mass: 0.5% of nano cuprous oxide (20-120nm), 4.5% of titanium dioxide and 95% of master batch polypropylene (PP), stirring for 15min at the normal temperature at 1500r/min in a high-speed stirrer to obtain a mixture, transferring the mixture to a double-screw extruder, and carrying out melting, cooling, cutting and granulation at 180 ℃ to obtain nano cuprous oxide antibacterial polypropylene master batch M4, wherein the nano cuprous oxide antibacterial polypropylene master batch M4 is yellow green.
Step three, preparing the antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: 40.64 percent of nano cuprous oxide antibacterial polypropylene master batch M and 99.36 percent of melt-blown polypropylene are subjected to mixing, storage hopper, 240 ℃ screw extrusion melting, high-pressure melt conveying, filtering, air flow traction, spinning, net forming, coiling and finished product forming to obtain the antibacterial melt-blown non-woven fabric which is white.
Example 5
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
step one, the nano cuprous oxide is prepared in the same way as the step one of the embodiment 1.
Step two, preparing the nano cuprous oxide antibacterial polypropylene master batch M5, namely mixing the following raw materials in percentage by mass: 0.5% of nano cuprous oxide (20-120nm), 4.5% of barium sulfate powder and 95% of master batch polypropylene (PP), stirring for 15min at normal temperature at 1500r/min in a high-speed stirrer to obtain a mixture, transferring the mixture to a double-screw extruder, and carrying out melting, cooling, cutting and granulation at 180 ℃ to obtain nano cuprous oxide antibacterial polypropylene master batch M5, wherein the nano cuprous oxide antibacterial polypropylene master batch M5 is yellow-green.
Step three, preparing the antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: the preparation method comprises the following steps of mixing the nano cuprous oxide antibacterial polypropylene master batch M50.64%, melt-blowing the polypropylene 99.36%, extruding and melting by a screw at 240 ℃, conveying by a high-pressure melt, filtering, air-flow drawing, spinning, net-forming, coiling and obtaining the finished product, thus obtaining the antibacterial melt-blown non-woven fabric which is white.
Example 6
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
step one, the nano cuprous oxide is prepared in the same way as the step one of the embodiment 1.
Step two, preparing the nano cuprous oxide antibacterial polypropylene master batch M6, namely mixing the following raw materials in percentage by mass: 0.5% of nano cuprous oxide (20-120nm), 4.5% of calcium carbonate powder and 95% of master batch polypropylene (PP), stirring for 15min at the normal temperature at 1500r/min in a high-speed stirrer to obtain a mixture, transferring the mixture to a double-screw extruder, and carrying out melting, cooling, cutting and granulation at 180 ℃ to obtain nano cuprous oxide antibacterial polypropylene master batch M6, wherein the nano cuprous oxide antibacterial polypropylene master batch M6 is yellow-green.
Step three, preparing the antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: the preparation method comprises the following steps of mixing 60.64% of nano cuprous oxide antibacterial polypropylene master batch and 99.36% of melt-blown polypropylene, extruding and melting by a screw at 240 ℃, conveying by a high-pressure melt, filtering, drawing by an air flow, spinning, forming a net, coiling and obtaining a finished product to obtain the antibacterial melt-blown non-woven fabric, wherein the antibacterial melt-blown non-woven fabric is white.
Example 7
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
step one, the nano cuprous oxide is prepared in the same way as the step one of the embodiment 1.
Step two, preparing the nano cuprous oxide antibacterial polypropylene master batch M7, namely mixing the following raw materials in percentage by mass: 0.5% of nano cuprous oxide (20-120nm), 4.5% of zirconium hydrogen phosphate powder and 95% of master batch polypropylene, stirring for 15min at normal temperature in a high-speed stirrer at 1500r/min to obtain a mixture, transferring the mixture to a double-screw extruder, and performing melting, cooling, cutting and granulation at 180 ℃ to obtain nano cuprous oxide antibacterial polypropylene master batch M7, wherein the nano cuprous oxide antibacterial polypropylene master batch M7 is yellow-green.
Step three, preparing the antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: 70.64 percent of nano cuprous oxide antibacterial polypropylene master batch and 99.36 percent of melt-blown polypropylene are subjected to mixing, storage hopper, 240 ℃ screw extrusion melting, high-pressure melt conveying, filtering, air flow traction, spinning, net forming, coiling and finished product forming to obtain the antibacterial melt-blown non-woven fabric which is white.
Example 8
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
step one, the nano cuprous oxide is prepared in the same way as the step one of the embodiment 1.
Step two, preparing the nano cuprous oxide antibacterial polypropylene master batch M8, namely mixing the following raw materials in percentage by mass: 2.5% of nano cuprous oxide (20-120nm), 47.5% of zeolite powder and 50% of master batch polypropylene, stirring for 15min at normal temperature in a high-speed stirrer at 1500r/min to obtain a mixture, transferring the mixture to a double-screw extruder, and performing melting, cooling, cutting and granulation at 180 ℃ to obtain nano cuprous oxide antibacterial polypropylene master batch M8, wherein the nano cuprous oxide antibacterial polypropylene master batch M8 is yellow-green.
Step three, preparing the antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: the preparation method comprises the following steps of mixing the nano cuprous oxide antibacterial polypropylene master batch M84%, melting the melt-blown polypropylene 96%, extruding and melting by a screw at 240 ℃, conveying by a high-pressure melt, filtering, drawing by an air flow, spinning, forming a net, coiling and obtaining a finished product to obtain the antibacterial melt-blown non-woven fabric, wherein the antibacterial melt-blown non-woven fabric is white.
Example 9
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
step one, the nano cuprous oxide is prepared in the same way as the step one of the embodiment 1.
Step two, preparing the nano cuprous oxide antibacterial polypropylene master batch M9, namely mixing the following raw materials in percentage by mass: 2.5% of nano cuprous oxide (20-120nm), 47.5% of talcum powder and 50% of master batch polypropylene, stirring for 15min at normal temperature in a high-speed stirrer at 1500r/min to obtain a mixture, transferring the mixture to a double-screw extruder, and performing melting, cooling, cutting and granulation at 180 ℃ to obtain nano cuprous oxide antibacterial polypropylene master batch M9, wherein the nano cuprous oxide antibacterial polypropylene master batch M9 is yellow-green.
Step three, preparing the antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: the preparation method comprises the following steps of mixing the nano cuprous oxide antibacterial polypropylene master batch M94%, melting the melt-blown polypropylene 96%, extruding and melting by a screw at 240 ℃, conveying by a high-pressure melt, filtering, drawing by an air flow, spinning, forming a net, coiling and obtaining a finished product to obtain the antibacterial melt-blown non-woven fabric, wherein the antibacterial melt-blown non-woven fabric is white.
Example 10
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
step one, the nano cuprous oxide is prepared in the same way as the step one of the embodiment 1.
Step two, preparing the nano cuprous oxide antibacterial polypropylene master batch M10, namely mixing the following raw materials in percentage by mass: 2.5% of nano cuprous oxide (20-120nm), 47.5% of kaolin and 50% of master batch polypropylene, stirring for 15min at the normal temperature in a high-speed stirrer at 1500r/min to obtain a mixture, transferring the mixture to a double-screw extruder, and performing melting, cooling, cutting and granulation at 180 ℃ to obtain nano cuprous oxide antibacterial polypropylene master batch M10, wherein the nano cuprous oxide antibacterial polypropylene master batch M10 is yellow-green.
Step three, preparing the antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: the preparation method comprises the following steps of mixing the nano cuprous oxide antibacterial polypropylene master batch M104% and the melt-blown polypropylene 96%, extruding and melting by a screw at 240 ℃, conveying by a high-pressure melt, filtering, drawing by an air flow, spinning, forming a net, coiling and obtaining a finished product to obtain the antibacterial melt-blown non-woven fabric, wherein the antibacterial melt-blown non-woven fabric is white.
Example 11
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
step one, the nano cuprous oxide is prepared in the same way as the step one of the embodiment 1.
Step two, preparing the nano cuprous oxide antibacterial polypropylene master batch M11, namely mixing the following raw materials in percentage by mass: 2.5% of nano cuprous oxide (20-120nm), 47.5% of titanium dioxide and 50% of master batch polypropylene, stirring for 15min at the normal temperature in a high-speed stirrer at 1500r/min to obtain a mixture, transferring the mixture to a double-screw extruder, and carrying out melting, cooling, cutting and granulation at 180 ℃ to obtain nano cuprous oxide antibacterial polypropylene master batch M11, wherein the nano cuprous oxide antibacterial polypropylene master batch M11 is yellow-green.
Step three, preparing the antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: the preparation method comprises the following steps of mixing the nanometer cuprous oxide antibacterial polypropylene master batch M114%, melt-blowing the polypropylene 96%, extruding and melting by a screw at 240 ℃, conveying by a high-pressure melt, filtering, drawing by an air flow, spinning, forming a net, coiling and obtaining a finished product to obtain the antibacterial melt-blown non-woven fabric, wherein the antibacterial melt-blown non-woven fabric is white.
Example 12
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
step one, the nano cuprous oxide is prepared in the same way as the step one of the embodiment 1.
Step two, preparing the nano cuprous oxide antibacterial polypropylene master batch M12, namely mixing the following raw materials in percentage by mass: 2.5% of nano cuprous oxide (20-120nm), 47.5% of barium sulfate powder and 50% of master batch polypropylene PP, stirring for 15min at normal temperature at 1500r/min in a high-speed stirrer to obtain a mixture, transferring the mixture to a double-screw extruder, and carrying out melting, cooling, cutting and granulation at 180 ℃ to obtain nano cuprous oxide antibacterial polypropylene master batch M12, wherein the nano cuprous oxide antibacterial polypropylene master batch M12 is yellow-green.
Step three, preparing the antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: the preparation method comprises the following steps of mixing the nanometer cuprous oxide antibacterial polypropylene master batch M124%, melt-blowing the polypropylene 96%, extruding and melting by a screw at 240 ℃, conveying a high-pressure melt, filtering, drawing by an air flow, spinning, forming a net, coiling and obtaining a finished product to obtain the antibacterial melt-blown non-woven fabric, wherein the antibacterial melt-blown non-woven fabric is white.
Example 13
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
step one, the nano cuprous oxide is prepared in the same way as the step one of the embodiment 1.
Step two, preparing the nano cuprous oxide antibacterial polypropylene master batch M13, namely mixing the following raw materials in percentage by mass: 2.5% of nano cuprous oxide (20-120nm), 47.5% of calcium carbonate powder and 50% of master batch polypropylene (PP), stirring for 15min at the normal temperature at 1500r/min in a high-speed stirrer to obtain a mixture, transferring the mixture to a double-screw extruder, and carrying out melting, cooling, cutting and granulation at 180 ℃ to obtain nano cuprous oxide antibacterial polypropylene master batch M13, wherein the nano cuprous oxide antibacterial polypropylene master batch M13 is yellow-green.
Step three, preparing the antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: m134% of nano cuprous oxide antibacterial polypropylene master batch and 96% of melt-blown polypropylene are subjected to mixing, storage hopper, extrusion melting by screw at 240 ℃, high-pressure melt conveying, filtering, air flow traction, spinning, web forming, coiling and finished product forming to obtain the antibacterial melt-blown non-woven fabric which is white.
Example 14
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
the method comprises the following steps: the nano cuprous oxide is prepared by the same step one as the example 1.
Step two, preparing the nano cuprous oxide antibacterial polypropylene master batch M14, namely mixing the following raw materials in percentage by mass: 2.5% of nano cuprous oxide (20-120nm), 47.5% of zirconium hydrogen phosphate powder and 50% of master batch polypropylene PP, stirring for 15min at normal temperature at 1500r/min in a high-speed stirrer to obtain a mixture, transferring the mixture to a double-screw extruder, and carrying out melting, cooling, cutting and granulation at 180 ℃ to obtain nano cuprous oxide antibacterial polypropylene master batch M14, wherein the nano cuprous oxide antibacterial polypropylene master batch M14 is yellow-green.
Step three, preparing the antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: the preparation method comprises the following steps of mixing M144% of nano cuprous oxide antibacterial polypropylene master batch and 96% of polypropylene PP, extruding and melting by a screw at 240 ℃, conveying by a high-pressure melt, filtering, drawing by an air flow, spinning, forming a net, coiling and obtaining a finished product to obtain the antibacterial melt-blown non-woven fabric, wherein the antibacterial melt-blown non-woven fabric is white.
Example 15
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
the method comprises the following steps: preparation of nano cuprous oxide (60-120 nm): feeding the copper acetate solution and the potassium hydroxide solution according to a molar mass ratio of 1:2, reacting at 25 ℃, stirring for 1 hour, and filtering to obtain blue filter residue. Feeding the blue filter residue and an ascorbic acid solution according to a molar mass ratio of 5:1, carrying out suction filtration to obtain yellow filter residue, carrying out vacuum drying at 90 ℃ for 6 hours, and collecting to obtain nano cuprous oxide which is orange yellow, wherein the reaction temperature is 25 ℃, the stirring time is 24 hours.
Step two, in the same way as the step two of example 14, the nano cuprous oxide antibacterial polypropylene masterbatch M15 is prepared, and the nano cuprous oxide antibacterial polypropylene masterbatch M15 is yellow.
Step three, in the same manner as in step three of example 14, an antibacterial meltblown nonwoven fabric was obtained, which was white.
The micro-morphology of the nano cuprous oxide in the first determination step is a round cake shape, the particle size is 60-120nm, the result is shown in fig. 5, and the XRD is shown in 2# in fig. 2.
Example 16
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
step one, preparing nano cuprous oxide (20-120 nm): feeding a copper chloride solution and a sodium hydroxide solution according to a molar mass ratio of 1:2, reacting at 25 ℃, stirring for 1 hour, and filtering to obtain blue filter residue. Feeding the blue filter residue and a sodium borohydride solution according to a molar mass ratio of 100:1, carrying out suction filtration to obtain yellow-green filter residue, carrying out vacuum drying at 90 ℃ for 6 hours, and collecting nano cuprous oxide which is yellow-green, wherein the reaction temperature is 25 ℃, the stirring time is 24 hours.
Step two, the same as the step two of the example 1, the nano cuprous oxide antibacterial polypropylene master batch M16 is prepared, and the nano cuprous oxide antibacterial polypropylene master batch M16 is yellow.
And step three, obtaining the antibacterial melt-blown non-woven fabric in the same way as the step three in the embodiment 1, wherein the antibacterial melt-blown non-woven fabric is white.
Example 17
The embodiment of the application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
step one, preparing nano cuprous oxide (20-120 nm): feeding a copper chloride solution and a sodium hydroxide solution according to a molar mass ratio of 1:2, reacting at 25 ℃, stirring for 1 hour, and filtering to obtain blue filter residue. Feeding the blue filter residue and a sodium borohydride solution according to a molar mass ratio of 1:1, carrying out suction filtration to obtain yellow-green filter residue, carrying out vacuum drying at 90 ℃ for 6 hours, and collecting nano cuprous oxide which is yellow-green, wherein the reaction temperature is 25 ℃, the stirring time is 24 hours.
Step two, the same as the step two of the example 1, the nano cuprous oxide antibacterial polypropylene master batch M17 is prepared, and the nano cuprous oxide antibacterial polypropylene master batch M17 is yellow.
And step three, obtaining the antibacterial melt-blown non-woven fabric in the same way as the step three in the embodiment 1, wherein the antibacterial melt-blown non-woven fabric is white.
Comparative example 1
The application comparative example provides a micron order brick red cuprous oxide master batch antibacterial melt-blown non-woven fabric, and the specific preparation comprises:
step one, preparing brick red cuprous oxide micron particle composite antibacterial mildew-proof PP master batch: mixing the following raw materials in percentage by mass: 2.5% of brick red micron-sized cuprous oxide, 47.5% of zirconium hydrogen phosphate powder and 50% of master batch polypropylene (PP), stirring for 15min at normal temperature at 1500r/min in a high-speed stirrer to obtain a mixture, transferring the mixture to a double-screw extruder, and carrying out melting, cooling, cutting and granulating at 180 ℃ to obtain the brick red cuprous oxide master batch.
Step two, preparing the micron-sized brick red cuprous oxide master batch antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: 4% of brick red cuprous oxide master batch and 96% of melt-blown polypropylene, and obtaining the light-red-brown antibacterial non-woven fabric by mixing, storing a hopper, extruding and melting by a screw at 240 ℃, conveying a high-pressure melt, filtering, air-flow drawing, spinning, forming a net, coiling and forming a finished product.
Comparative example 2
The application comparative example provides a micron order brick red cuprous oxide master batch antibacterial melt-blown non-woven fabric, and the specific preparation comprises:
mixing the following raw materials in percentage by mass: 0.5 percent of brick red micron-sized cuprous oxide and 99.5 percent of melt-blown polypropylene are subjected to material mixing, storage hopper, 240 ℃ screw extrusion melting, high-pressure melt conveying, filtering, air flow traction, spinning, net forming, coiling and finished product forming to obtain the reddish-brown antibacterial non-woven fabric.
Comparative example 3
The application provides a nano-scale yellowish green cuprous oxide powder antibacterial melt-blown non-woven fabric, and the specific preparation comprises the following steps:
mixing the following raw materials in percentage by mass: 0.5% of yellowish green nano-scale cuprous oxide (20-120nm) prepared in the step one of the embodiment 1 and 99.5% of melt-blown polypropylene are subjected to mixing, storage hopper, extrusion melting by screw at 240 ℃, high-pressure melt conveying, filtering, air flow traction, spinning, web forming, coiling and finished product treatment to obtain the yellowish antibacterial non-woven fabric.
Comparative example 4
The application comparative example provides a nano-silver antibacterial melt-blown non-woven fabric, and the specific preparation comprises the following steps:
step one, preparing nano-silver antibacterial polypropylene master batch by mixing the following raw materials in percentage by mass: 5% of silver nitrate, 91% of zirconium phosphate powder and 4% of zinc oxide, stirring for 15min at normal temperature in a high-speed stirrer at 1500r/min to obtain a mixture, transferring the mixture to a double-screw extruder, and performing melting, cooling, cutting and granulation at 180 ℃ to obtain the white nano-silver antibacterial polypropylene master batch.
Step two, preparing the nano-silver antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: 4% of nano-silver antibacterial polypropylene master batch and 96% of melt-blown polypropylene, and the white antibacterial non-woven fabric is obtained by mixing, storing a hopper, extruding and melting by a screw at 240 ℃, conveying by high-pressure melt, filtering, air-flow drawing, spinning, forming a net, coiling and forming a finished product.
Comparative example 5
The application provides a nano cuprous oxide antibacterial polypropylene master batch and an antibacterial melt-blown non-woven fabric, and the specific preparation method comprises the following steps:
step one, preparing nano cuprous oxide (200-: feeding a copper chloride solution and a sodium hydroxide solution according to a molar mass ratio of 1:2, reacting at 25 ℃, stirring for 1 hour, and filtering to obtain blue filter residue. Mixing blue filter residue and ascorbic acid solution according to a molar mass ratio of 1:2, feeding materials, wherein the reaction temperature is 37 ℃, the stirring time is 12 hours, filtering to obtain yellow-green filter residues, drying in vacuum at 90 ℃ for 6 hours, and collecting to obtain nano cuprous oxide which is orange.
Step two, preparing the nano cuprous oxide antibacterial polypropylene master batch M18: mixing the following raw materials in percentage by mass: 0.5% of nano cuprous oxide (200-300nm), 4.5% of zeolite powder and 95% of master batch polypropylene (PP), stirring for 15min at normal temperature at 1500r/min in a high-speed stirrer to obtain a mixture, transferring the mixture to a double-screw extruder, and performing melting, cooling, cutting and granulation at 180 ℃ to obtain nano cuprous oxide antibacterial polypropylene master batch M18, wherein the nano cuprous oxide antibacterial polypropylene master batch M18 is orange yellow.
Step three, preparing the antibacterial melt-blown non-woven fabric: mixing the following raw materials in percentage by mass: the preparation method comprises the following steps of mixing the nano cuprous oxide antibacterial polypropylene master batch M180.64%, melt-blowing the polypropylene 99.36%, extruding and melting by a screw at 240 ℃, conveying by a high-pressure melt, filtering, air-flow drawing, spinning, net-forming, coiling and obtaining the finished product, thus obtaining the antibacterial melt-blown non-woven fabric which is white.
Test example 1
The test examples of the present application are the antibacterial meltblown nonwoven fabric filtration test of examples 1 to 17 and comparative examples 1 to 5, and the results are shown in table 1.
Filtration test of Table 1 the filtration test was performed according to conventional practice
Test example 2
The test examples of the application are the antibacterial performance test and the mildewproof effect evaluation of the antibacterial melt-blown non-woven fabrics of the above examples 1 to 17 and the comparative examples 1 to 5, and the antibacterial performance test and the mildewproof effect evaluation are respectively carried out according to the following national standards: the antibacterial performance test of the plastic master batch and the plastic plate is carried out according to GB/T31402-2015, and the test strains are escherichia coli AS 1.90 and staphylococcus aureus ACTT 6538P; the national standard of the antibacterial plastic plate is that the antibacterial agent/nano cuprous oxide antibacterial polypropylene master batch is added into the resin raw material to prepare the antibacterial modified plastic plate, the bacteriostasis rate of the antibacterial modified plastic plate is more than 90%, and the test results are shown in the following table 2.
TABLE 2
The evaluation of the mildew-proof effect of the antibacterial melt-blown nonwoven fabrics of examples 1 to 17 and comparative examples 1 to 5 was carried out according to GB/T24128-2018, test strains: aspergillus niger CGMCC3.3928, paecilomyces variotii CGMCC3.4253, Chaetomium globosum CGMCC3.3601, Trichoderma longibrachiatum ACTT13631 and Penicillium funiculosum CGMCC3.3875, wherein the mildew-proof grade is defined as follows: stage 0-no production, stage 1-trace growth (long mold area < 10% observed under microscope), stage 2-small growth (10% ≦ long mold area < 30%), stage 3-medium growth (30% ≦ long mold area < 60%), stage 4-heavy growth (60% ≦ long mold area ≦ 100%) the results of the tests are shown in table 3 below.
TABLE 3
Test example 3
The test example of the application is the cytotoxicity test of the antibacterial melt-blown non-woven fabric of the embodiment 1, and is in accordance with the national standard GB/T16886.5-2007. Example 1 the effect of the antimicrobial meltblown nonwoven (examples 1-7, typical of example 1, with a 32ppm cuprous oxide content in the polypropylene layer) on the activity of mouse fibroblasts was evaluated to assess the magnitude of cytotoxicity.
In the test, two test systems, namely a serum-containing culture medium and a serum-free culture medium, are used for in vitro cytotoxicity evaluation of the test sample. The sample volume of each well is 100 mu L, the optical density value of each well is determined under the conditions of measuring wavelength of 570nm and reference wavelength of 650nm after the contact treatment with the cells for about 24h, and the survival rate of each group of cells is calculated according to a calculation formula.
The test result shows that, according to GB/T16886.5-2017, under the condition of the research, 32ppm of the antibacterial melt-blown non-woven fabric leaching liquor of the serum/serum-free culture medium sample represented by example 1 has no cytotoxicity.
From the test examples, the antibacterial melt-blown non-woven fabric is white, the filter effect is more than 99%, the antibacterial effect is more than 99%, the mildew resistance is 0 level, the content of the nano cuprous oxide antibacterial polypropylene master batch in the antibacterial melt-blown non-woven fabric is as low as 6.4 per thousand (w/w), the net content of the nano cuprous oxide is as low as 32ppm, and the antibacterial melt-blown non-woven fabric is completely nontoxic due to the extremely low addition amount, so that the antibacterial melt-blown non-woven fabric has good biological safety.
The foregoing is only a preferred embodiment of the present application and it should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.
Claims (10)
1. An antibacterial mildew-proof melt-blown non-woven fabric is characterized by being prepared by the following preparation method:
mixing the nano cuprous oxide antibacterial polypropylene master batch with melt-blown polypropylene, and performing melt filtration, air flow traction, spinning, web formation, coiling and finished product after melt extrusion to obtain the antibacterial and mildewproof melt-blown non-woven fabric;
the preparation method of the nano cuprous oxide antibacterial polypropylene master batch comprises the following steps:
step 1, mixing soluble copper salt and alkali liquor for reaction, and carrying out solid-liquid separation to obtain a solid reactant; mixing the solid reactant with a reducing agent for reaction, and carrying out solid-liquid separation and drying to obtain nano cuprous oxide; the particle size of the nano cuprous oxide is 20-120 nm;
and 2, mechanically mixing the nano cuprous oxide, the high-temperature-resistant filler and the master batch polypropylene, performing melt extrusion, and then granulating to obtain the nano cuprous oxide antibacterial polypropylene master batch.
2. The antibacterial and mildewproof melt-blown non-woven fabric according to claim 1, wherein the nano cuprous oxide antibacterial polypropylene master batch and the melt-blown polypropylene are calculated according to the mass percentage and comprise
0.64 to 4 percent of nano cuprous oxide antibacterial polypropylene master batch;
96-99.36% of melt-blown polypropylene.
3. The antibacterial melt-blown nonwoven fabric according to claim 1, wherein in step 1, the soluble copper salt is selected from copper chloride or/and copper acetate; the alkali liquor is selected from sodium hydroxide solution or/and potassium hydroxide solution.
4. The antibacterial meltblown nonwoven fabric according to claim 1, wherein in step 1 the reducing agent is selected from sodium borohydride and/or ascorbic acid.
5. The antibacterial melt-blown non-woven fabric according to claim 1, wherein in the step 1, the molar mass ratio of the soluble copper salt to the alkali liquor is 1 (1.5-3.5).
6. The antibacterial melt-blown nonwoven fabric according to claim 1, wherein in the step 1, the molar mass ratio of the solid reactant to the reducing agent is 1 (0.01-1).
7. The antibacterial melt-blown nonwoven fabric according to claim 1, wherein in the step 2, the high-temperature-resistant filler is selected from one or more of natural zeolite, artificial zeolite, kaolin, talcum powder, titanium dioxide, barium sulfate powder, calcium carbonate powder and zirconium hydrogen phosphate.
8. The antibacterial and mildewproof melt-blown non-woven fabric as claimed in claim 1, wherein the melt index of the melt-blown polypropylene is 1000-1900g/10 min.
9. The antibacterial and mildewproof melt-blown non-woven fabric according to claim 1, wherein in the step 2, the melt index of the master batch polypropylene is 30-40g/10 min.
10. The antibacterial and mildewproof melt-blown non-woven fabric according to claim 1, wherein in the step 2, the nano cuprous oxide antibacterial polypropylene master batch comprises the following components in percentage by mass
0.5 to 2.5 percent of nano cuprous oxide;
4.5 to 47.5 percent of high-temperature resistant filler;
50-95% of master batch polypropylene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539625A (en) * | 2022-02-28 | 2022-05-27 | 广东粤港澳大湾区国家纳米科技创新研究院 | Nano-gold antibacterial powder, antibacterial plastic master batch or material, preparation method and application |
| CN115467083A (en) * | 2022-09-29 | 2022-12-13 | 广东粤港澳大湾区国家纳米科技创新研究院 | Degradable antibacterial non-woven fabric and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013142215A (en) * | 2012-01-12 | 2013-07-22 | Nippon Ion Kk | Antimicrobial melt-blown nonwoven fabric and method for producing the same |
| CN103992562A (en) * | 2014-05-16 | 2014-08-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Halogen-free flame-retardant antibacterial anti-aging polypropylene composite material and preparation method thereof |
| CN104804113A (en) * | 2015-04-22 | 2015-07-29 | 上海恒洁生物科技有限公司 | Alloy antibacterial masterbatch and application thereof to yarn |
| CN104984592A (en) * | 2015-07-07 | 2015-10-21 | 沈海波 | Composite material capable of resisting and inhibiting bacteria, absorbing dust and filtering dust and manufacturing method of composite material |
| CN108385183A (en) * | 2018-02-10 | 2018-08-10 | 海盐县硕创服装研究所 | Hydrophilic polypropylene fiber and preparation method thereof |
| US20200115511A1 (en) * | 2017-05-11 | 2020-04-16 | Zhejiang Yinyu New Material Co., Ltd | A method for preparing masterbatch and fiber with composite antibacterial and deodorizing functions |
| CN112831860A (en) * | 2021-01-15 | 2021-05-25 | 广东广油华丰科技研究有限公司 | Melt-blown non-woven fabric with sterilization and bacteriostasis functions and preparation method thereof |
| CN112921503A (en) * | 2021-01-20 | 2021-06-08 | 胡晨 | Inactivated germ melt-blown fabric and production process thereof |
| CN113307300A (en) * | 2021-06-01 | 2021-08-27 | 广东粤港澳大湾区国家纳米科技创新研究院 | Nano cuprous oxide and preparation method and application thereof |
| CN113337903A (en) * | 2021-06-01 | 2021-09-03 | 鹤山市东海塑料色母有限公司 | Antiviral polypropylene non-woven fabric and preparation method thereof |
-
2021
- 2021-09-30 CN CN202111163561.XA patent/CN113684611A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013142215A (en) * | 2012-01-12 | 2013-07-22 | Nippon Ion Kk | Antimicrobial melt-blown nonwoven fabric and method for producing the same |
| CN103992562A (en) * | 2014-05-16 | 2014-08-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Halogen-free flame-retardant antibacterial anti-aging polypropylene composite material and preparation method thereof |
| CN104804113A (en) * | 2015-04-22 | 2015-07-29 | 上海恒洁生物科技有限公司 | Alloy antibacterial masterbatch and application thereof to yarn |
| CN104984592A (en) * | 2015-07-07 | 2015-10-21 | 沈海波 | Composite material capable of resisting and inhibiting bacteria, absorbing dust and filtering dust and manufacturing method of composite material |
| US20200115511A1 (en) * | 2017-05-11 | 2020-04-16 | Zhejiang Yinyu New Material Co., Ltd | A method for preparing masterbatch and fiber with composite antibacterial and deodorizing functions |
| CN108385183A (en) * | 2018-02-10 | 2018-08-10 | 海盐县硕创服装研究所 | Hydrophilic polypropylene fiber and preparation method thereof |
| CN112831860A (en) * | 2021-01-15 | 2021-05-25 | 广东广油华丰科技研究有限公司 | Melt-blown non-woven fabric with sterilization and bacteriostasis functions and preparation method thereof |
| CN112921503A (en) * | 2021-01-20 | 2021-06-08 | 胡晨 | Inactivated germ melt-blown fabric and production process thereof |
| CN113307300A (en) * | 2021-06-01 | 2021-08-27 | 广东粤港澳大湾区国家纳米科技创新研究院 | Nano cuprous oxide and preparation method and application thereof |
| CN113337903A (en) * | 2021-06-01 | 2021-09-03 | 鹤山市东海塑料色母有限公司 | Antiviral polypropylene non-woven fabric and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539625A (en) * | 2022-02-28 | 2022-05-27 | 广东粤港澳大湾区国家纳米科技创新研究院 | Nano-gold antibacterial powder, antibacterial plastic master batch or material, preparation method and application |
| CN114539625B (en) * | 2022-02-28 | 2023-12-05 | 广东粤港澳大湾区国家纳米科技创新研究院 | Antibacterial nano gold powder, antibacterial plastic master batch or material, preparation method and application |
| CN115467083A (en) * | 2022-09-29 | 2022-12-13 | 广东粤港澳大湾区国家纳米科技创新研究院 | Degradable antibacterial non-woven fabric and preparation method thereof |
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