CN1296550C - Modified nano oxide compound, its application and use thereof - Google Patents
Modified nano oxide compound, its application and use thereof Download PDFInfo
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- CN1296550C CN1296550C CNB2004100673991A CN200410067399A CN1296550C CN 1296550 C CN1296550 C CN 1296550C CN B2004100673991 A CNB2004100673991 A CN B2004100673991A CN 200410067399 A CN200410067399 A CN 200410067399A CN 1296550 C CN1296550 C CN 1296550C
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Abstract
The present invention relates to a method for preparing modified nano oxide and a purpose thereof for a function finishing agent. The modified nano oxide has the following structural formula as a formula I, wherein A is nano oxide which is nano titanium oxide, nano zinc oxide, nano alumina, nano ferric oxide and nano silicon oxide and the compound of the nano titanium oxide, the nano zinc oxide, the nano alumina, the nano ferric oxide and the nano silicon oxide; R is equal to (CH2)n, and n is equal to 0 to 4; Y is vinyl, hydroxy, aminoalkyl, amido, epoxy group, methacryloyl oxyalkyl or sulfhydryl. The modified nano oxide has the following structural formula as a formula II, wherein m is equal to 0 to 20, R is equal to A, H and the alkyl group of C1-C4. The modified nano oxide is prepared by means that the nano oxide reacts with a modifying agent to be emulsified and can be used for preparing the function finishing agent. Natural fibers which are finished by the modified nano oxide have the functions of ultraviolet resistance and bacterium resistance.
Description
Technical field
The invention belongs to after-finishing of textile products auxiliary agent technical field.Relate to modified nano oxide compound, preparation method and as the purposes of finishing functions of textile fabrics agent.
Background technology
Nanometer technology is the priority research areas comparatively paid close attention to of countries in the world in recent years, has obtained bigger progress to the technology of preparing of nano-oxide at the end of last century, and some nano-scale oxides have been realized industrialized production.Because the particle size of nanometer oxide particle (powder) is very little, has great surface ratio, often cause the sudden change of its physics character, the quantum size effect of nano material and skin effect, make and itself have the not available optical characteristics of bulky grain material, ultraviolet and infrared ray are had extremely strong reflection characteristic, be added on and have anti-ultraviolet aging in the material, and the heat-insulation and heat-preservation effect; The small-size effect of nano material and macro quanta tunnel effect will increase substantially intensity, elasticity, resistance to water, photostability and the heat endurance of material; The profuse residual bond of nano-material surface makes it have superpower surface-activity, and the pigment particle is had superpower absorption protective effect, will reduce the pigment decay that causes because of the ultraviolet ray irradiation widely.For example the silver-plated nano particle has extremely strong broad-spectrum antimicrobial effect, and to the human body totally nontoxic; Nano zine oxide and Titanium particles have good absorption and uv reflectance ability, can effectively prevent the generation of illnesss such as cutaneum carcinoma; The nano zircite monoclinic crystal, can absorb outside energy effectively, and the radiation far infrared identical with the human body biological wave wave spectrum, act on the people and know from experience celliferous resonance activation phenomenon, have insulation and antibacterial, stimulate circulation, health care effect such as enhancing immunity; Other also has the various nano particles of functions such as far infrared, negative oxygen ion, fluorescence.These characteristics of nano-oxide, the different field in machinery, electronics, chemical industry, the energy, biology, national defence and daily life has obtained application.Nano material is applied to textile industry, can produces functional fiber and fabric, can give performances such as fabric uvioresistant, antibiotic, infra-red radiation.
But the nano-oxide specific area is big, surface-activity is high, and high surface energy makes it be easy to reunite bad dispersibility; In addition, nano-oxide belongs to inorganic material, and belongs to organic textile fabric, especially natural fabric is not had compatibility, and nanoparticle can't form firm chemical bond combination with fiber.Therefore, nano particle being evenly dispersed on the textiles, and realizing that nano particle combines with the strong of fiber, is the key technology of nano-function textile development and application.The present invention adopts certain chemical method that nano-oxide and nano composite oxide surface are carried out necessary chemical modification, introduce groups such as hydroxyl, amino, siloxy, make simple nano particle or simple nanometer organic matter " cluster " with reactive group, improve nano particle the dispersion stabilization of aqueous phase and with the reactivity of natural fabric, and can be by grafting or crosslinked method, by the back arrangement modified nano oxide compound particle is applied on the natural fabric, obtains the finishing functions effect of durability.
At present, the nano-oxide surface modifying method is mainly contained: (1) solution deposition seasoning at nano-oxide surface deposition layer of metal oxide or moisture metal oxide, changes its surface chemical property.(2) surfactant method adopts CATION or anion surfactant modification, forms the outside clad of hydrocarbon chain in nanoparticle surface, makes the nanoparticle surface oleophylicization.(3) coupling agent method, utilizing titanium system or silicon is the coupling agent treatment nano-oxide, can improve the dispersed and stable of dispersion.(4) polymer overmold method is handled nano particle by polymer overmold, forms the solvation barrier layer, hinders nano particle and reunites because of the cloth youth moves to collide mutually.Also have surface reaction method, chemical precipitation method in addition.
The modification of above-mentioned nano-oxide mainly is to carry out in the preparation, has improved the dispersion behavior of nanoparticle in medium, but does not solve the fastness that combines of nanoparticle and fiber.It is reported, can obtain the function of durability in order to make natural fabric, can utilize the group on the technology activation fibers such as non-thermal plasma trap, corona discharge and combination takes place, but factory's actual production need increase new equipment, production cost increases.
Summary of the invention
The object of the invention provides a kind of modified nano oxide compound.
Another object of the present invention provides a kind of preparation method of above-mentioned modified nano oxide compound.
Purpose of the present invention also provides the purposes of a kind of above-mentioned modified nano oxide compound as the finishing functions of textile fabrics agent.
The present invention adopts chemical method, nano-oxide is carried out finishing, make the simple modified nano oxide compound with reactive group, this nano-oxide can produce the chemical bond combination by the hydroxyl on suitable crosslinking agent or grafting agent and the natural fabric, carboxyl, amino isoreactivity group.
The preparation of modified nano oxide compound disperses nano-oxide with appropriate organic solvent, organic solvent is selected for use and contained polyhydroxy, especially contains the organic solvent of 2 ~ 5 hydroxyls; Add an amount of dispersant, especially macromolecule dispersing agent, disperse with high-speed emulsifying machine and ultrasonic oscillation device; Add surface modifier, surface modifier is selected for use and is contained the different active group of two classes, and class active group energy and inorganic nanometer oxide reaction form chemical bond or self condensation; Another kind of active group energy and suitable crosslinking agent or grafting agent reaction form covalent bond, also can or pass through suitable radical reaction on crosslinking agent or grafting agent and the natural fabric, form covalent bond.Add suitable dispersant again, regulate suitable pH value, be prepared into modified nano oxide compound dispersion liquid with quite stable.
Modified nano oxide compound of the present invention can be represented by the formula:
Wherein, A is a nano-oxide, can be nano-titanium oxide, nano zine oxide, nano aluminium oxide, nano-sized iron oxide, nano silicon oxide and their compound thereof, as nano-titanium oxide-zinc oxide composites, nano aluminium oxide-iron oxide compound etc.; R=(CH
2) n, n=0～4; Y is the organic group that energy and organic matter react, as, vinyl, hydroxyl, aminoalkyl, amino, epoxy radicals, methacryl oxyalkyl, sulfydryl etc.
Wherein, m=0～20, R "=A, H or C
1～C
4Alkyl.
From the reflection of said structure formula, surface modifier can form oligomer in the condensation of nano-oxide surface dewatering.By changing the mol ratio of surface modifier and nano-oxide reaction, the degree of polymerization of oligomer is between 1～20.
The preparation method of modified nano oxide compound of the present invention, be that nano-oxide is disperseed with the polyhydroxy organic solvent of selecting for use that contains, especially contain the organic solvent of 2～5 hydroxyls, special recommendation contains the alcohol of 2～3 hydroxyls, as, ethylene glycol, glycerol, propylene glycol, diethylene glycol etc.Add an amount of dispersant, especially macromolecule dispersing agent,, disperse with high-speed emulsifying machine and ultrasonic oscillation device as triethanolamine, polyethylene glycol, polyacrylamide, polyvinylpyrrolidone etc.; Add surface modifier, surface modifier is selected for use and is contained the different active group of two classes, and class group energy and inorganic nanometer oxide reaction form chemical bond or self condensation, as acetoxyl group, methoxyl group, ethyoxyl, carboxymethyl cellulose etc.; Another kind of active group can and suitable crosslinking agent or grafting agent reaction, form covalent bond, also can with suitable radical reaction on the natural fabric, the formation covalent bond is as vinyl, hydroxyl, aminoalkyl, amino, epoxy radicals, methacryloxy, sulfydryl etc.Add suitable dispersant again, as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty alcohol-polyoxyethylene ether, alkylsulfonates etc. are regulated the pH value, are prepared into the modified nano oxide compound dispersion liquid with quite stable.
The preparation method of modified nano oxide compound of the present invention specifically can be divided into three processes:
1, nano-oxide is dispersed into primary particle
Adopt suitable method that the aggregate of nano-oxide is smashed, be dispersed into primary particle.Key is to select appropriate organic solvent, the present invention selects for use and contains polyhydric organic solvent, especially the organic solvent that contains 2～5 hydroxyls, special recommendation contains the alcohol of 2～3 hydroxyls, as ethylene glycol, glycerol, propylene glycol, diethylene glycol etc. and suitable dispersant, as polyethylene glycol, poly amic acid, polyvinylpyrrolidone etc.Described nano-oxide can be nano-titanium oxide, nano zine oxide, nano aluminium oxide, nano-sized iron oxide, nano silicon oxide and their compound thereof, as nano-titanium oxide-zinc oxide composites, nano-titanium oxide-silica compound, nano aluminium oxide-iron oxide compound etc.
Decentralized medium: select for use to contain the polyhydroxy organic solvent, especially contain the organic solvent of 2～5 hydroxyls, special recommendation contains the alcohol of 2～3 hydroxyls, as ethylene glycol, glycerol, propylene glycol, diethylene glycol etc.
Dispersant: select suitable dispersant for use, macromolecule dispersing agent especially is as triethanolamine, polyethylene glycol, polyacrylamide, polyvinylpyrrolidone etc.
The nano-oxide that above-mentioned nano-oxide, dispersant and polyalcohol is disperseed to obtain primary particle at high speed dispersor or supersonic oscillations instrument.The percentage by weight of nano-oxide and dispersant and polyalcohol is respectively 10～35% and 5～25%.As adopt high speed dispersor, be advisable for rotating speed 10000-50000 rev/min.
2, modification
At 40 ℃～100 ℃, special recommendation obtained the nano-oxide of modification in 1～4 hour 70 ℃～90 ℃ reactions with the dispersion liquid of the nano-oxide of above-mentioned primary particle and modifier.The mol ratio of modifier and nano-oxide is 0.1～1: 1.
Described modifier is to contain the different reactive group of two classes in the molecule, and class active group energy and inorganic nanometer oxide reaction form chemical bond or self condensation, as acetoxyl group, methoxyl group, ethyoxyl etc.; Another kind of active group energy and suitable crosslinking agent or grafting agent reaction, form covalent bond, also can with suitable radical reaction on the natural fabric, form covalent bond, as vinyl, hydroxyl, aminoalkyl, amino, epoxy radicals, methacryl oxyalkyl, sulfydryl etc.As organic silicone couplet, can be represented by the formula:
Y-R-SiX
3
Y is the organic group that energy and organic matter react, as, vinyl, hydroxyl, aminoalkyl, amino, epoxy radicals, methacryl oxyalkyl, sulfydryl etc.
X is a hydrolyzable groups, as acetoxyl group, methoxyl group, ethyoxyl etc.
3, emulsification obtains stable modified nano oxide compound emulsion
The further emulsification of the nano-oxide of modification obtains stable modified nano oxide compound emulsion.In the nano-oxide of the modification of above-mentioned gained, add emulsifying agent, 20～60 ℃ of reactions 30～90 minutes.Described emulsifying agent can be a polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty alcohol-polyoxyethylene ether, alkylsulfonate etc.The emulsifying agent consumption is 5～15g/L.Regulate pH=2～7 with acetic acid.
Modified nano oxide compound of the present invention not only preparation method is easy, and can be used as the finishing functions of textile fabrics agent easily.To comprise natural fabrics such as COTTON FABRIC, ramie fabric, sodolin, silk fabric, wool fabric can adopt conventional roll, dry by the fire, roasting technology carries out multi-functional arrangement.Finish fabric after testing, anti-ultraviolet property, all greater than 99%, the Ultraviolet Protection Factor of fabric reaches more than the 45-50 to the shielding rate of UVA and UVB.Press the test of FZ/T 01021-92 antibacterial fabric method for testing performance, gram-positive bacteria and Gram-negative bacteria typical case bacterial classification are all had tangible antibacterial action, antimicrobial efficiency reaches more than 90%.Finish fabric ability standard is washed more than 50 times.
The present invention will be helped further to understand by following embodiment, but content of the present invention can not be limited.
The specific embodiment
The preparation of embodiment 1 modified nano-titanium dioxide
1, disperses
Rutile-phase nano-titanium dioxide 20 grams, 70 milliliters of organic solvent ethylene glycol and polyethylene of dispersing agent pyrrolidones 15 grams are mixed, disperse with high speed dispersor, 10000～30000 rev/mins of rotating speeds are used supersonic oscillations simultaneously.30 ~ 60 minutes time.
2, modification
Surface modifier gamma-aminopropyl-triethoxy-silane 20 grams are joined in the above-mentioned dispersion, stirred 10 minutes, add 40 ml waters, stirred 30 minutes, be warming up to 80～100 ℃, reacted 2～4 hours.
3, emulsification
3 gram emulsifying agent peregals 0 are joined in the above-mentioned reactant, use the vinegar acid for adjusting pH value, make pH=4～6,1000～3000 rev/mins of mixing speeds, 30～60 minutes time, 20～60 ℃ of temperature.
The preparation of embodiment 2 modification composite nano oxides
1, disperses
With the nano-oxide of different proportion, as nano-ZnO and nano-TiO
2Mix at 1～3: 3～1 by weight proportion, gets and mix nano-oxide 20 grams, 70 milliliters of glycerol, polyvinylpyrrolidone 10 grams, polyethylene glycol (M=400) 2 grams disperse with high speed dispersor, 10000～30000 rev/mins of rotating speeds are used supersonic oscillations simultaneously, 30～60 minutes time.
2, modification
Surface modifier γ-glycidoxy methoxy silane 15 grams are joined in the above-mentioned dispersion, stirred 10 minutes, add 30 ml waters, stirred 30 minutes, be warming up to 80～100 ℃, reacted 2～4 hours.
3, emulsification
4 gram emulsifier ELs are joined in the above-mentioned reactant, use the vinegar acid for adjusting pH value, make pH=4～7,1000～3000 rev/mins of mixing speeds, time 30-60 minute, 20～60 ℃ of temperature.
The preparation of embodiment 3 modified nano zinc oxides
1, disperses
Nano zine oxide 20 grams, 70 milliliters of organic solvent diethylene glycols and dispersant polyacrylamide 10 grams are mixed, disperse with high speed dispersor, 10000 ~ 30000 rev/mins of rotating speeds are used supersonic oscillations simultaneously, 30～60 minutes time.
2, modification
Surface modifier gamma-methyl allyl acyloxypropyl trimethoxysilane 20 grams are joined in the above-mentioned dispersion, stirred 10 minutes, add 30 ml waters, stirred 30 minutes, be warming up to 80～100 ℃, reacted 2～4 hours.
3, emulsification
3 gram polyoxyethylene nonylphenol ethers are joined in the above-mentioned reactant, use the vinegar acid for adjusting pH value, make pH=4～6,1000～3000 rev/mins of mixing speeds, 30～60 minutes time, 20～60 ℃ of temperature.
The processing of embodiment 4 anti-ultraviolet finishing pure cotton fabrics
The dressing liquid prescription:
Embodiment 1 finishing agent 7.5g/L
Modification 2D resin 80g/L
MgCl
2 0.1g/L
Bleeding agent 0.05-0.1g/L
Finishing technique:
The pure cotton dyeing plain cloth, number 30 * 30, density 68 * 68.Two soak two rolls dressing liquid, pick-up rate 80～100%, and 100～105 ℃ of preliminary dryings 2～5 minutes, 120～150 ℃ baked 2～4 minutes, washing, oven dry.
Finishing effect sees Table 1.
The anti-ultraviolet property of table 1 anti-ultraviolet finishing pure cotton fabric
| Sample number into spectrum | Treatment conditions | Testing result | |
| Ultraviolet ray transmissivity | Protecting factor | ||
| 1 2 | The control fabric finish fabric | UVB 3.02％ UVA 2.95％ UVB 1.15％ UVA 1.07％ | UPF＝34 UPF≥50 |
Annotate: press GB/T 18830-2002 fabric ultraviolet resistance measurement of test method.
The processing of example 5 antibacterial functions ramie fabrics
The dressing liquid prescription:
Embodiment 3 finishing agent 7.5g/L
Fixparet FR-ECO 80g/L
MgCl
2 5g/L
Bleeding agent 0.05-0.1g/L
Finishing technique:
Pure ramie fabric, number 36 * 36, density 54 * 54 are handled through destarch, bleaching.Two soak two rolls dressing liquid, pick-up rate 70～80%, and 60 ℃ of preliminary dryings 3 minutes, 120 ~ 150 ℃ baked 2～4 minutes, and washing is soaped, washing, oven dry.
Finishing effect sees Table 2.
The anti-microbial property of the antibiotic ramie fabric of table 2
| Treatment conditions | Bacterial classification | Total plate count (* 10 4Individual/mL) | Bacterium reduces percentage (%) | |
| 0 contact | Cultivated 22 hours | |||
| Untreated fabric finish fabric untreated fabric finish fabric | Esherichia coli staphylococcus aureus staphylococcus aureus | 2.63 0.17 2.51 1.33 | 0.02 0.119 | 98.6 93.8 |
Annotate: press the test of FZ/T 01021-92 antibacterial fabric method for testing performance.
Example 6 multi-functional arrangement pure cotton fabric processing
(1) dressing liquid prescription:
Embodiment 2 finishing agent 7.5g/L
Grafting agent U-51 15g/L
Bleeding agent 0.05-0.1g/L
(2) finishing technique:
The pure cotton dyeing plain cloth, number 30 * 40, density 100 * 60.Two soak two rolls dressing liquid, pick-up rate 80～100%, and 100～105 ℃ of preliminary dryings 2～5 minutes, 120～150 ℃ baked 2～4 minutes, washing, oven dry.
The test of the finishing effect of multifunctional fabric sees Table 3 and table 4.
The anti-ultraviolet property of the multi-functional arrangement pure cotton fabric of table 3
| Sample number into spectrum | Treatment conditions | Testing result | |
| Ultraviolet ray transmissivity | Protecting factor | ||
| 1 2 3 | Control fabric TiO 2∶ZnO＝3∶1 TiO 2∶ZnO＝1∶3 | UVB 3.02％ UVA 2.95％ UVB 0.92％ UVA 0.85％ UVB 0.94％ UVA 0.92％ | UPF＝34 UPF≥50 UPF≥50 |
Annotate: press the test of FZ/T 01021-92 antibacterial fabric method for testing performance.
The anti-microbial property of the multi-functional arrangement pure cotton fabric of table 4
| Treatment conditions | Bacterial classification | Total plate count (* 10 4Individual/mL) | Bacterium reduces percentage (%) | |
| 0 contact | Cultivated 22 hours | |||
| Untreated fabric TiO 2∶ZnO＝1∶3 TiO 2: ZnO=3: 1 untreated fabric TiO 2∶ZnO＝1∶3 TiO 2∶ZnO＝3∶1 | Esherichia coli escherichia coli and staphylococcus aureus staphylococcus aureus staphylococcus aureus | 2.63 0.35 0.55 2.51 0.31 1.69 | 0 0.07 0.10 0.21 | 100 95.6 92.9 90.0 |
Annotate: press the test of FZ/T 01021-92 antibacterial fabric method for testing performance.
Claims (4)
1, a kind of preparation method of modified nano oxide compound is characterized in that making by following method:
(1) nano-oxide and the modifier with primary particle reacts the nano-oxide that obtained modification in 1～4 hour at 40 ℃～100 ℃; The mol ratio of modifier and nano-oxide is 0.1～1: 1;
Described modifier is represented with following formula:
Y-R-SiX
3
Y is vinyl, hydroxyl, aminoalkyl, amino, epoxy radicals, methacryl oxyalkyl or sulfydryl; X is the hydrolyzable organic group; R=(CH
2) n, n=0～4;
(2) in the nano-oxide of the modification of above-mentioned gained, add emulsifying agent, obtained stable modified nano oxide compound emulsion in 30-90 minute 20～60 ℃ of reactions; Described emulsifying agent is a polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty alcohol-polyoxyethylene ether or alkylsulfonate; The emulsifying agent consumption is 5-15g/L; Regulate pH=2-7 with acetic acid;
Described nano-oxide is nano-titanium oxide, nano zine oxide, nano aluminium oxide, nano-sized iron oxide, nano silicon oxide and their compound thereof.
2, the preparation method of a kind of modified nano oxide compound as claimed in claim 1 is characterized in that described hydrolyzable organic group is acetoxyl group, methoxy or ethoxy.
3, the preparation method of a kind of modified nano oxide compound as claimed in claim 1, the nano-oxide that it is characterized in that described primary particle is disperseed to obtain on high speed dispersor or supersonic oscillations instrument by nano-oxide, dispersant and polyalcohol, and nano-oxide and the dispersant percentage by weight in polyalcohol is respectively 10～35% and 5～25%;
Described polyalcohol is ethylene glycol, glycerol, propylene glycol or diethylene glycol; Described dispersant is polyethylene glycol, triethanolamine, polyacrylamide or polyvinylpyrrolidone; Described nano-oxide is nano-titanium oxide, nano zine oxide, nano aluminium oxide, nano-sized iron oxide, nano silicon oxide and nano-titanium oxide-nano oxidized zinc complexes, nano aluminium oxide-nano oxidized iron complexes or nano-titanium oxide-nano oxidized silicon compound.
4, a kind of preparation method of a kind of modified nano oxide compound as claimed in claim 1 is characterized in that being used for the multi-functional arrangement of textiles.
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| CNB2004100673991A CN1296550C (en) | 2004-10-22 | 2004-10-22 | Modified nano oxide compound, its application and use thereof |
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| CN100460332C (en) * | 2006-03-31 | 2009-02-11 | 北京化工大学 | Method for modifying titanium dioxide film by heterocyclic compound |
| CN101215430B (en) * | 2007-12-29 | 2010-07-21 | 株洲时代新材料科技股份有限公司 | Stabilization dispersion treatment method for nano aluminum oxide in organic solvent |
| CN102733174B (en) * | 2011-03-31 | 2015-02-25 | 香港理工大学 | Method for finishing fabrics |
| CN102277722A (en) * | 2011-05-12 | 2011-12-14 | 安徽工程大学 | Modified nanometer oxide, preparation method and use method of self-emulsified dispersive liquid thereof |
| CN102660154A (en) * | 2012-04-28 | 2012-09-12 | 常州大学 | Surface modification method for nanometer titanium dioxide |
| CN103114455B (en) * | 2013-01-25 | 2014-12-10 | 杭州贝斯特化纤有限公司 | Auxiliary agent for regenerative polyester fibers with combined function and preparation method thereof |
| CN103360801B (en) * | 2013-07-22 | 2015-07-01 | 华南理工大学 | Novel nano-fluid and its preparation method and application thereof |
| CN103572584B (en) * | 2013-10-09 | 2016-04-06 | 江南大学 | There is the preparation method of the modified nano-titanium dioxide finishing agent of uvioresistant and automatically cleaning double effects |
| CN103881421B (en) * | 2014-03-07 | 2015-07-22 | 江苏双乐化工颜料有限公司 | Nanometer surface modifier and preparation method and using method thereof |
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| CN108560259B (en) * | 2018-04-18 | 2021-09-10 | 上海工程技术大学 | Method for improving bonding fastness of nano ZnO on modified polyester fabric |
| CN111519313B (en) * | 2020-04-30 | 2021-04-13 | 深圳华域佳泰纺织科技有限公司 | Nano metal antibacterial fiber fabric and preparation method thereof |
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| CN113755035B (en) * | 2021-09-28 | 2022-07-26 | 亚士创能科技(上海)股份有限公司 | Epoxy silane modified nano alumina and polymer cement-based waterproof coating |
| CN114808186A (en) * | 2022-03-19 | 2022-07-29 | 苏州美纳福健康科技有限公司 | Antibacterial fiber, dry and wet dual-purpose antibacterial non-woven fabric and preparation method |
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