CN115418851A - Preparation method of graphene antibacterial composite fabric - Google Patents
Preparation method of graphene antibacterial composite fabric Download PDFInfo
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- CN115418851A CN115418851A CN202211034928.2A CN202211034928A CN115418851A CN 115418851 A CN115418851 A CN 115418851A CN 202211034928 A CN202211034928 A CN 202211034928A CN 115418851 A CN115418851 A CN 115418851A
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- fabric
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- antibacterial
- graphene
- padding
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- 239000004744 fabric Substances 0.000 title claims abstract description 78
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000000835 fiber Substances 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 150000002500 ions Chemical class 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 17
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 12
- 230000014759 maintenance of location Effects 0.000 claims abstract description 11
- 239000004902 Softening Agent Substances 0.000 claims abstract description 8
- 239000012209 synthetic fiber Substances 0.000 claims abstract description 8
- 229920002994 synthetic fiber Polymers 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 238000010025 steaming Methods 0.000 claims abstract description 6
- 125000002091 cationic group Chemical group 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- -1 quaternary ammonium salt cation Chemical class 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 239000011787 zinc oxide Substances 0.000 claims description 10
- 239000005751 Copper oxide Substances 0.000 claims description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 102000004190 Enzymes Human genes 0.000 claims description 6
- 108090000790 Enzymes Proteins 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 229940112669 cuprous oxide Drugs 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000000149 penetrating effect Effects 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 229920003169 water-soluble polymer Polymers 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical class CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 2
- PYFNMTXVGCHGMU-UHFFFAOYSA-N chloromethylbenzene;pyridine Chemical compound C1=CC=NC=C1.ClCC1=CC=CC=C1 PYFNMTXVGCHGMU-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 13
- 238000007670 refining Methods 0.000 description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 241000222122 Candida albicans Species 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 3
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 3
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- 235000009120 camo Nutrition 0.000 description 3
- 235000005607 chanvre indien Nutrition 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011487 hemp Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- GNPSDJOWGWWXSS-UHFFFAOYSA-M 1-benzylpyridin-1-ium;chloride Chemical group [Cl-].C=1C=CC=C[N+]=1CC1=CC=CC=C1 GNPSDJOWGWWXSS-UHFFFAOYSA-M 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 229940048053 acrylate Drugs 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- ZVYPQQRJQLEUJV-UHFFFAOYSA-N butyl prop-2-enoate;prop-2-enamide;prop-2-enoic acid Chemical compound NC(=O)C=C.OC(=O)C=C.CCCCOC(=O)C=C ZVYPQQRJQLEUJV-UHFFFAOYSA-N 0.000 description 2
- 229940095731 candida albicans Drugs 0.000 description 2
- 235000012343 cottonseed oil Nutrition 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000001814 pectin Substances 0.000 description 2
- 235000010987 pectin Nutrition 0.000 description 2
- 229920001277 pectin Polymers 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/203—Unsaturated carboxylic acids; Anhydrides, halides or salts thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
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- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/47—Compounds containing quaternary nitrogen atoms derived from heterocyclic compounds
- D06M13/477—Compounds containing quaternary nitrogen atoms derived from heterocyclic compounds having six-membered heterocyclic rings
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- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to a preparation method of a graphene antibacterial composite fabric, which comprises the following steps: (1) pretreatment: immersing the yarns of the fabric into a groove containing a pretreatment agent solution for padding retention treatment to remove impurities in the yarns of the fabric, and then washing and drying; (2) ion grafting-antibacterial finishing padding: introducing a quaternary ammonium salt-containing cationic solution for ion grafting treatment, drying, and introducing an antibacterial finishing agent solution for padding treatment; the antibacterial finishing agent solution comprises graphene and copper-zinc particles; (3) After ion grafting-antibacterial finishing is carried out on the fabric of the natural fiber, pre-drying is carried out, and then wet short steaming treatment is carried out to obtain the graphene antibacterial composite fabric; after ion grafting-antibacterial finishing, the synthetic fiber fabric is subjected to four-stage baking treatment, then is introduced into a softening agent solution for padding, and is shaped to obtain the graphene antibacterial composite fabric. The method has the effect of high antibacterial fastness after multiple times of washing.
Description
Technical Field
The invention relates to the technical field of textile surface modification, in particular to a preparation method of a graphene antibacterial composite fabric.
Background
The increasing demand inherent to hygiene today drives the rapid growth of the antimicrobial fabric market. In the prior art, the processing means of the antibacterial fabric generally adopts silver ion sterilization, and the antibacterial fabric is obtained by soaking the antibacterial fabric in a silver ion finishing agent and adsorbing silver ions on the surface of fabric fibers. However, this processing method is generally not resistant to washing and has poor fastness, and the antibacterial property is basically lost after washing with water frequently. In the prior art, the fabric with the antibacterial coating is usually obtained by coating the surface of the fabric, however, the application of the coating usually deteriorates the air permeability of the fabric.
In addition, silver ions, especially nano silver, are potentially harmful because they act in a free or released manner, and when excessive, they cannot be discharged from the human body, which may result in poisoning, causing concerns about environmental safety and human health, and thus, the application of silver ion antibacterial agents to medical devices has been clearly prohibited. And as an antibacterial fabric in contact with the human body, there is inevitably a potential hazard.
Therefore, the antibacterial problem of the fabric is mainly solved: 1. searching a finishing agent capable of replacing a silver ion antibacterial agent; 2. on the premise of keeping the air permeability of the fabric, the antibacterial fastness of the fabric after washing is high.
Disclosure of Invention
In order to solve the technical problems, a preparation method of the graphene antibacterial composite fabric is provided. The method has the effect of high antibacterial fastness after multiple times of washing.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a graphene antibacterial composite fabric comprises the following steps:
(1) Pretreatment: immersing the yarns of the fabric into a groove containing a pretreatment agent solution for padding retention treatment to remove impurities in the yarns of the fabric, and then washing and drying;
(2) Ion grafting-antibacterial finishing padding: introducing the yarn of the pretreated fabric into a cationic solution containing quaternary ammonium salt for ion grafting treatment, drying, and introducing into an antibacterial finishing agent solution for padding treatment;
the antibacterial finishing agent solution comprises the following materials in 100% by weight: 3-10% of graphene, 1-15% of copper-zinc particles, 5-40% of a cross-linking agent, 1-5% of a hyperdispersant, 0.5-3% of a surfactant and the balance of water;
(3) After the ion grafting-antibacterial finishing is carried out on the fabric of the natural fiber, pre-drying is carried out firstly, and then the graphene antibacterial composite fabric is obtained after wet short steaming processing;
after the ion grafting-antibacterial finishing is carried out on the synthetic fiber fabric, four-stage baking treatment is carried out, then the synthetic fiber fabric is introduced into a softening agent solution for padding, and the graphene antibacterial composite fabric is obtained after shaping.
Further, the fabric is natural fiber or synthetic fiber, impurities in yarn of the natural fiber are pectin, cotton wax, cottonseed hulls, hemp husks and the like, and impurities in yarn of the synthetic fiber are slurry, spinning oil and the like; the pretreatment agent solution for the fabric of the natural fiber comprises the following materials in percentage by weight of 100 percent: 2-20% of refined enzyme, 25-55% of sodium hydroxide, 0.5-2% of dimethyl tetramethylidene sodium phosphate, 1-5% of refined penetrating agent and the balance of water, wherein the pretreatment process for the natural fiber fabric is padding retention treatment or ultrasonic padding retention treatment; the pretreatment agent solution for the fabric of the natural fiber is water and/or alcohol, and the pretreatment process must be matched with ultrasonic padding retention treatment; the frequency of the ultrasonic wave is 2-5 MHz.
Furthermore, the ion grafting-antibacterial finishing padding process also comprises the step of adopting ultrasonic assistance; the ultrasonic wave frequency of the ultrasonic wave assistance is 2-5 MHz.
Further, the pretreatment agent solution for the natural fiber comprises the following materials in 100% by weight: 2-20% of refining enzyme, 25-55% of sodium hydroxide, 0.5-2% of dimethyl tetramethylidene sodium phosphate, 1-5% of refining penetrating agent and the balance of water.
Further, the drying temperature in the step (1) and the step (2) is 50-100 ℃; the quaternary ammonium salt cation-containing solution is obtained by dissolving a quaternary ammonium salt surfactant in water and/or ethanol, and the concentration of the quaternary ammonium salt cation-containing solution is (5-12) g/L; the quaternary ammonium salt surfactant is one or more of dialkyl dimethyl ammonium salt, alkyl trimethyl ammonium salt and benzyl chloride pyridinium salt.
Further, the graphene is graphene oxide of 500-800 nanometers; the zinc-copper particles are a mixture of at least one of nano copper oxide and nano cuprous oxide and nano zinc oxide in any mass ratio;
further, the cross-linking agent is acrylate; the hyper-dispersant is an acrylate water-soluble polymer dispersant; the surfactant is nonionic surfactant, and the nonionic surfactant is one or more of JFC, JFC-1, JFC-2 and JFC-E, JFC-S. The cross-linking agent has the cross-linking function of firmly attaching the antibacterial material to the fiber, and can also make the fabric have better hand feeling; the nonionic surfactant functions to permeate the antibacterial material into the interstices of the fibers.
Further, the pre-drying temperature is 85-102 ℃, and the time is 1-2min; the wet short steaming process treatment is carried out at 140 ℃ for 0.5-1.5min.
Further, the four-stage baking treatment is temperature treatment in four stages, namely 90 +/-5 ℃ treatment for 1-2min, 160 +/-5 ℃ treatment for 1-2min, 190 +/-5 ℃ treatment for 1-2min and 120 +/-5 ℃ treatment for 1-2min; the softening agent solution is an organic silicon softening agent with the mass concentration of 2-10%. The four-stage baking treatment is more uniform in heating and has less damage to fibers.
The beneficial technical effects are as follows:
according to the invention, quaternary ammonium salt cation grafting is firstly carried out on the fabric, so that ionic bonds are anchored on yarn fibers of the fabric, and then antibacterial finishing of the formula is carried out, so that the antibacterial material is anchored and extends into fiber gaps through the ionic bonds, thus the long-acting antibacterial and water-washing-resistant effect is obtained, and the antibacterial fabric prepared by the method disclosed by the invention is repeatedly washed, so that the attenuation of the antibacterial effect is less than 2%, and the antibacterial and water-washing-resistant performance is better. According to the invention, graphene and zinc-copper particles are used as antibacterial materials, so that the antibacterial rate of the finished fabric to Candida albicans can reach more than 98% after repeated water washing, and the antibacterial rate to Staphylococcus aureus can reach more than 99.5%.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. 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 invention.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards; if no corresponding national standard exists, the method is carried out according to the universal international standard or the standard requirement proposed by related enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
The refining enzyme, the refining enzyme penetrant, the silicone softener, etc. used in the following examples are regarded as substances used in conventional technical means unless otherwise specified, and those skilled in the art know the above types of substances conventionally used in the industry.
Example 1
A preparation method of a graphene antibacterial composite fabric comprises the following steps:
(1) Pretreatment: immersing the yarn of the cotton-flax fiber into a groove containing a pretreatment agent solution for padding retention treatment to remove impurities such as pectin, cotton wax, cottonseed hulls, hemp husks and the like in the fiber yarn, then washing with water and drying at the temperature of below 100 ℃;
the pretreatment agent solution comprises the following materials in 100 percent by weight: 10% of refining enzyme, 35% of sodium hydroxide, 1% of dimethyl tetramethylidene sodium phosphate, 3% of refining penetrating agent and the balance of water.
(2) Ion grafting-antibacterial finishing padding: dissolving a quaternary ammonium salt surfactant in water and ethanol (the volume ratio of the water to the ethanol is 2:1) to obtain the quaternary ammonium salt cation-containing solution with the concentration of 10g/L, wherein the quaternary ammonium salt surfactant is benzyl pyridinium chloride; immersing the pretreated cotton and hemp fiber yarns into the quaternary ammonium salt cation-containing solution for ion grafting treatment, immersing and mixing the fiber fabrics and the quaternary ammonium salt cation-containing solution according to the proportion of 10mL, drying at the temperature of below 100 ℃, and introducing an antibacterial finishing agent solution to be matched with 2-5 MHz ultrasonic wave for padding treatment for 12 seconds;
the antibacterial finishing agent solution comprises the following materials in 100% by weight: 5% of graphene, 12% of zinc-copper particles, 10% of cross-linking agent sodium acrylate, 2% of acrylic acid-butyl acrylate-acrylamide terpolymer water-soluble polymer dispersant, 0.8% of JFC-2 nonionic surfactant and the balance of water;
wherein the graphene is graphene oxide with the average particle size of 500-800 nm; the zinc-copper particles are nano zinc oxide and nano copper oxide (equal mass ratio).
(3) After the cotton-flax fibers are subjected to ion grafting-antibacterial finishing padding in the previous step, pre-drying is carried out for 1-2min at 100 ℃, and then wet short steaming processing is carried out for 1min at 140 ℃ to obtain the graphene antibacterial composite cotton-flax fabric.
Example 2
The preparation method of this example is the same as that of example 1, except that the zinc-copper particles in the antibacterial finishing agent solution are a mixture of nano zinc oxide and nano cuprous oxide prepared in equal proportion.
Example 3
The preparation method of this example is the same as that of example 1, except that the zinc-copper particles in the antibacterial finishing agent solution are a mixture of nano zinc oxide, nano copper oxide and nano cuprous oxide prepared in equal proportion.
Example 4
A preparation method of a graphene antibacterial composite fabric comprises the following steps:
(1) Pretreatment: immersing the yarn of the polyester fiber into a groove containing a pretreatment agent solution, carrying out padding retention treatment for 12 seconds by adopting 2-5 MHz ultrasonic wave assistance to remove impurities such as sizing agent, oil agent and the like in the yarn of the polyester fiber, then washing with water, and drying at the temperature of below 100 ℃;
the pretreatment agent solution is a mixed solution of water and ethanol (the volume ratio is 2:1).
(2) Ion grafting-antibacterial finishing padding: dissolving a quaternary ammonium salt surfactant in water and ethanol (the volume ratio of the water to the ethanol is 2:1) to obtain the quaternary ammonium salt cation-containing solution with the concentration of 10g/L, wherein the quaternary ammonium salt surfactant is benzyl pyridinium chloride; immersing the pretreated polyester fiber yarn into a quaternary ammonium salt cation-containing solution for ion grafting treatment, immersing and mixing a fiber fabric and the quaternary ammonium salt cation-containing solution according to the proportion of 1g to 10mL, drying at the temperature of below 100 ℃, and introducing an antibacterial finishing agent solution to be matched with 2-5 MHz ultrasonic wave for padding treatment for 12 seconds;
the antibacterial finishing agent solution comprises the following materials in percentage by weight of 100 percent: 10% of graphene, 3% of zinc-copper particles, 35% of a cross-linking agent sodium acrylate, 3% of an acrylic acid-butyl acrylate-acrylamide terpolymer water-soluble polymer dispersant, 3% of a JFC-2 nonionic surfactant and the balance of water;
wherein the graphene is graphene oxide with the average particle size of 500-800 nm; the zinc-copper particles are nano zinc oxide and nano copper oxide (equal mass ratio).
(3) After the polyester fiber is subjected to ion grafting-antibacterial finishing padding in the previous step, four-stage baking treatment is carried out: treating at 90 +/-5 ℃ for 2min, at 160 +/-5 ℃ for 1min, at 190 +/-5 ℃ for 1min, and at 120 +/-5 ℃ for 2min, then introducing an organic silicon softening agent solution with the concentration of 5% for padding treatment, and shaping at 180 +/-5 ℃ to obtain the graphene antibacterial composite fabric.
Comparative example 1
The comparative example was prepared in the same manner as in example 1, except that in step (2), the cationic solution containing quaternary ammonium salt and the antimicrobial finishing agent solution were mixed and then the fabric was subjected to the ultrasonic-assisted padding treatment.
Comparative example 2
The comparative example was prepared in the same manner as in example 1, except that the zinc-copper particles in the antimicrobial finish solution were exclusively nano-zinc oxide.
Comparative example 3
The comparative example was prepared in the same manner as example 1, except that the zinc-copper particles in the antimicrobial finish solution were exclusively nano-copper oxide.
Comparative example 4
The preparation method of the comparative example is the same as that of example 1, except that the antibacterial finishing agent solution does not contain graphene, and zinc-copper particles are added according to the weight percentage of the graphene.
The antibacterial performance of the antibacterial fabric obtained in the above examples and comparative examples is tested before washing, and then the antibacterial performance of the antibacterial fabric is tested after washing for 30 times, the washing procedure is carried out according to appendix C of FZ/T73023-2006, the antibacterial performance test is carried out by referring to part 3 of the oscillating method for GB/T20944.3-2008 textile antibacterial performance evaluation, and the test results are shown in Table 1.
TABLE 1 antibacterial property before and after washing of antibacterial fabric obtained in examples and comparative examples
As can be seen from Table 1, the antibacterial fabric prepared by the method disclosed by the invention has the antibacterial effect attenuated by less than 1% after repeated washing, has better antibacterial and water-washing resistance, has the antibacterial rate on Candida albicans of more than 98% and Staphylococcus aureus of more than 99.5% after repeated washing, and can completely meet the standard of AA-grade antibacterial fabrics. In the preparation method of comparative example 1, quaternary ammonium salt cations are not grafted, so that the antibacterial property of the fabric is seriously reduced after repeated washing. In comparative examples 2 and 3, only nano zinc oxide and nano copper oxide were used, respectively, and the degree of decrease in the resistance of the fabric after repeated washing, particularly the resistance to the fungus candida albicans, exceeded 2%. Comparative example 4 contains no graphene but nano copper oxide and nano zinc oxide, and the fabric has poor resistance to fungi and still good resistance to bacteria in an unwashed state, but the resistance to fungi after repeated washing is also greatly reduced. The graphene, the nano zinc oxide and the nano copper oxide are added to play a synergistic antibacterial role on bacteria and fungi, and the method disclosed by the invention has a very good washing resistance effect.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. A preparation method of a graphene antibacterial composite fabric is characterized by comprising the following steps:
(1) Pretreatment: immersing the yarns of the fabric into a groove containing a pretreatment agent solution for padding retention treatment to remove impurities in the yarns of the fabric, and then washing and drying;
(2) Ion grafting-antibacterial finishing padding: introducing the yarn of the pretreated fabric into a cationic solution containing quaternary ammonium salt for ion grafting treatment, drying, and introducing into an antibacterial finishing agent solution for padding treatment;
the antibacterial finishing agent solution comprises the following materials in 100% by weight: 3-10% of graphene, 1-15% of copper-zinc particles, 5-40% of a cross-linking agent, 1-5% of a hyperdispersant, 0.5-3% of a surfactant and the balance of water;
(3) After the ion grafting-antibacterial finishing is carried out on the fabric of the natural fiber, pre-drying is carried out, and then the wet short steaming process treatment is carried out, so that the graphene antibacterial composite fabric is obtained;
after the ion grafting-antibacterial finishing is carried out on the synthetic fiber fabric, four-stage baking treatment is carried out, then the synthetic fiber fabric is introduced into a softening agent solution for padding, and the graphene antibacterial composite fabric is obtained after shaping.
2. The preparation method of the graphene antibacterial composite fabric according to claim 1, wherein the fabric is a fabric of natural fibers or a fabric of synthetic fibers; the pretreatment agent solution for the fabric of the natural fiber comprises the following materials in percentage by weight of 100 percent: 2-20% of refined enzyme, 25-55% of sodium hydroxide, 0.5-2% of dimethyl tetramethylidene sodium phosphate, 1-5% of refined penetrating agent and the balance of water, wherein the pretreatment process for the natural fiber fabric is padding retention treatment or ultrasonic padding retention treatment; the pretreatment agent solution for the fabric of the natural fiber is water and/or alcohol, and the pretreatment process must be matched with ultrasonic padding retention treatment; the frequency of the ultrasonic wave is 2-5 MHz.
3. The preparation method of the graphene antibacterial composite fabric according to claim 1, wherein the ion grafting-antibacterial finishing padding process further comprises the steps of adopting ultrasonic assistance; the ultrasonic wave frequency of the ultrasonic wave assistance is 2-5 MHz.
4. The preparation method of the graphene antibacterial composite fabric according to claim 1, wherein the drying temperature in the steps (1) and (2) is 50-100 ℃; the quaternary ammonium salt cation-containing solution is obtained by dissolving a quaternary ammonium salt surfactant in water and/or ethanol, and the concentration of the quaternary ammonium salt cation-containing solution is (5-12) g/L; the quaternary ammonium salt surfactant is one or more of dialkyl dimethyl ammonium salt, alkyl trimethyl ammonium salt and benzyl chloride pyridinium salt.
5. The preparation method of the graphene antibacterial composite fabric according to claim 1, wherein the graphene is graphene oxide of 500-800 nm; the zinc-copper particles are a mixture of at least one of nano copper oxide and nano cuprous oxide and nano zinc oxide in any mass ratio.
6. The method for preparing the graphene antibacterial composite fabric according to claim 1, wherein the cross-linking agent is acrylate; the hyper-dispersant is an acrylate water-soluble polymer dispersant; the surfactant is a nonionic surfactant.
7. The preparation method of the graphene antibacterial composite fabric according to claim 1, wherein the pre-drying temperature is 85-102 ℃, and the time is 1-2min; the wet short steaming process treatment is carried out at 140 ℃ for 0.5-1.5min.
8. The method for preparing the graphene antibacterial composite fabric according to claim 1, wherein the four-stage baking treatment is a temperature treatment in four stages, namely 90 ± 5 ℃ treatment for 1-2min, 160 ± 5 ℃ treatment for 1-2min, 190 ± 5 ℃ treatment for 1-2min, and 120 ± 5 ℃ treatment for 1-2min; the softening agent solution is an organic silicon softening agent with the mass concentration of 2-10%.
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| CN112176746A (en) * | 2020-09-30 | 2021-01-05 | 谷令纺织科技(常州)有限公司 | Preparation method of natural fiber graphene composite material |
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| JPH07268780A (en) * | 1994-03-24 | 1995-10-17 | Matsui Shikiso Kagaku Kogyosho:Kk | Antimicrobial fiber products |
| KR19990044709A (en) * | 1998-03-30 | 1999-06-25 | 나재운 | Antimicrobial processing method of fiber or fabric including ultrasonic process |
| US20060251611A1 (en) * | 2003-12-23 | 2006-11-09 | Naruki Yamauchi | Antibacterial processing of fiber products |
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