CN104562658A - Amino acid nano-silver modified finishing agent as well as preparation method of finishing agent and modified fishing shell fabric - Google Patents
Amino acid nano-silver modified finishing agent as well as preparation method of finishing agent and modified fishing shell fabric Download PDFInfo
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Abstract
The invention provides an amino acid nano-silver modified finishing agent as well as a preparation method of the finishing agent and a modified fishing shell fabric. The amino acid nano-silver modified finishing agent is prepared by mixing a silver solution with an amino acid uniformly mixed solution and stirring the mixture for 30-45 minutes at 95-100 DEG C. The amino acid uniformly mixed solution is prepared by mixing an amino acid aqueous solution, a crosslinking agent and a surfactant. Fibers or a fabric of the fibers are dipped and rolled twice, roasted, washed and dried, so that the crease resistance, shrink resistance, the dye-uptake of the dye and the like of the modified finishing shell fabric are obviously improved and enhanced. The amino acid nano-silver modified finishing agent further has the technical advantages of simplified steps, environment-friendly process, closeness to nature and no pollution and short time.
Description
Technical field
That patent application of the present invention relates to is the modification agent of fiber and fabric thereof and the preparation method of modification agent, functional fiber through arranging modification and obtaining of fiber or its fabric or its fabric.
Background technology
Technical research shows, because Nano Silver has very high specific area and surface-activity, process based prediction model is stablized, and has superpower sterilization, bacteriostatic activity.Based on this, silver ion modification is implemented to fiber or its fabric, silver ion is adhered to be incorporated on cotton fiber body, cotton fiber is made to have anti-microbial property, this type of fabric-modifying, finishing technique have been seen in relevant public technology, but these modification technologies only obtain single antibacterial functions, and also with some other technical problem.As, technical scheme disclosed in Chinese patent CN201320262131, first scheme adopts Methacrylamide grafting process to cotton fiber, be graft by PMAm molecule, its structural electron rich group amido link again with silver ion coordination, improve cotton fiber to the suction-operated of silver ion, obtain the modified cotton fiber with anti-microbial property.There is the single technical deficiency of modified function in this programme, and will implement preliminary treatment to cotton fiber equally, and a whole set of modified technique is comparatively loaded down with trivial details, in addition, record according to its scheme, its water-fastness ability is poor, and the silver content reserved after modified cotton fiber washing is only original 75.23%.
Nano Silver is reduced by reductant to prepare, the reductant that prior art is generally selected includes sodium borohydride, hydrazine hydrate, glucose, ascorbic acid, sodium hypophosphite, natrium citricum etc., there is toxicity to a certain degree and carcinogenic in these reductant compositions of sodium borohydride, hydrazine hydrate, has potential harm to human body, other organism and environment.In the finishing functions of fabric, only obtain antibacterial functions with the Nano Silver of the reduction such as glucose, ascorbic acid preparation, reductant does not have function affect in the fabric arranged.
The development of technology will be catered to consumption demand and lead consumption guidance.Along with people deepen continuously to harmony between man and nature relation, the understanding of nature to Anthroposphere, natural materials composition is incorporated on fiber, produce, strengthen, extend and supplementary beneficial functions, remove, transform and weaken unfavorable factor, making it to present the New function of getting close to human body or other organism, is the development trend of weaving treatment technology.
Wherein, a kind of natural soluble bio-based materials---amino acid, with its biocompatibility, compatibility, containing natural NMF, there is the effect preventing skin aging, check melanin from generating, and safety, nontoxic natural quality, more and more attract attention by people in recent years.If implement amino-acid modified arrangement to fabric; moisture in energy available protecting fiber cuticula; play the effect of Glycerin; skin is made to keep delicacy, gloss and elasticity lastingly; it can be used as skin care adjustment of judogi fabric; be applied to underclothes, as underwear, shirt, bedding etc., in the application of ecological environment-friendly type hindlimb unload, show good application prospect.
Amino acid manifests to some extent at the finishing technique of cellulose base fiber fabric in prior art.Li Shaoquan etc. propose the modification technology COTTON FABRIC of carboxylated modification being implemented to the process of silk gum amino acid adsorbed in " preparation of the adsorbable material of COTTON FABRIC amino acid and sign thereof " literary composition.Though this technology completes the modification of silk gum amino acid to cotton fiber, the hydroscopicity of modification fabric improves a lot, but find that modified fabric exists the poor technical problem of washing fastness simultaneously, this be due between the carboxyl on amino acid whose amino and crafted cotton fibers for ionic bond is adsorbed, physical bond power is weak to be caused, in addition, modified cotton fabric fracture strength mechanical performance and whiteness are all in significantly declining, Boardy Feeling, comfort level is poor, another major technique defect of its technical scheme also needs before modified process to implement carboxylated modification preliminary treatment to cotton fiber, complex process, operation harmony is long, inefficiency.
Chinese patent CN 200710049287 openly describes portion and implements amino-acid modified technical scheme to synthetic fiber, in its scheme by amino acid graft copolymerization, blendedly enter in spinning solution in synthetic fiber material strand, the filament material spinned need through setting process, prepare a kind of containing amino acid whose profiled filament, amino acid is wherein changed by protein.The copolymerization of amino acid and synthetic fiber, blended in finished fiber, most amino acid merges and is distributed in fibrous inside, can very limited with skin contact, causes amino acid health function to be difficult to be given full play to comprehensively.
In sum, prior art ubiquity modified function is single, Function is limited, whole set process method belongs to degraded performance naturally, operation is loaded down with trivial details and the multiple technologies problem that fabric self-technique performance is also undesirable.
Summary of the invention
The goal of the invention of patent application of the present invention is to provide a kind of corpus fibrosum modified Nano silvery Preparation Method more leveling off to natural attribute and environmental requirement, the simultaneously naturally affine attribute of compatible amino acid, realization has multiple modified function and modified technique environmental protection, get close to nature, simplification, the amino acid nano-silver modification agent effectively improving the multinomial technical indicator of product and preparation method thereof and modification fabric.
The amino acid nano-silver modification agent technical scheme that patent application of the present invention provides, its main technical content is: the agent of a kind of amino acid nano-silver modification, this modification agent is pressed 1:1 volume ratio by silver-colored solution and the equal miscible fluid of amino acid and is mixed, obtained after stirring 30 ~ 45 minutes at 95 ~ 100 DEG C of temperature simultaneously, described silver-colored solution is the silver nitrate aqueous solution of 0.01 ~ 0.05g/L mass concentration scope, the equal miscible fluid of described amino acid is amino acid solution, the mixed solution that is uniformly dispersed of crosslinking agent and surfactant, the mass concentration of amino acid solution is wherein 20 ~ 60 g/L, crosslinking agent selects one of fatty alcohol glycidol ether or polybasic carboxylic acid, mass concentration is 20 ~ 60 g/L, surfactant is fatty alcohol-polyoxyethylene ether, its mass concentration is 2 ~ 6 g/L.
Patent application of the present invention also provides preparation method's technical scheme of described amino acid nano-silver modification agent, the method is: the equal miscible fluid of amino acid mixes by 1:1 volume ratio with silver-colored solution, stir 30 ~ 45 minutes at 95 ~ 100 DEG C of temperature simultaneously, obtained, wherein, described silver-colored solution is the silver nitrate aqueous solution of 0.01 ~ 0.05g/L mass concentration scope, the equal miscible fluid of described amino acid is amino acid solution, the mixed solution that is uniformly dispersed of crosslinking agent and surfactant, the mass concentration of amino acid solution is wherein 20 ~ 60 g/L, crosslinking agent selects one of fatty alcohol glycidol ether or polybasic carboxylic acid, mass concentration is 20 ~ 60 g/L, surfactant is fatty alcohol-polyoxyethylene ether, its mass concentration is 2 ~ 6 g/L.
In above-mentioned technical scheme, described fatty alcohol glycidol ether is one of any in hexylene glycol glycidol ether, butanediol diglycidyl ether, propylene glycol diglycidylether, ethylene glycol diglycidylether.
In above-mentioned technical scheme, described polybasic carboxylic acid is one of any in BTCA, citric acid, poly.
In above-mentioned technical scheme, described surfactant is one of any in Span-80, Tween80, JFC, paregal O.
In above-mentioned technical scheme, described amino acid solution to select in the aqueous solution such as lysine solution, glutamic acid aqueous solution or the methionine with good cost performance any one.
Patent application of the present invention additionally provides the modification fabric that the described amino acid nano-silver modification agent modification of application obtains, and corpus fibrosum alleged below or corpus fibrosum fabric are cotton fiber, viscose acetal fibre, tencel fiber, Modal fibre, bamboo fibre, flax fibre or its fabric.The modification method that the present patent application provides is: corpus fibrosum or corpus fibrosum fabric immerse in the agent of amino acid nano-silver modification, its bath raio is 1: 30, roll through two leachings two, each dipping 15 minutes, liquid carrying rate is 70 ~ 90%, by preliminary drying in 40 ~ 80 DEG C of temperature 5 minutes, then bake 3 minutes through 80 ~ 160 DEG C of temperature, be washed to neutrality, oven dry.
Amino acid nano-silver modification agent disclosed in patent application of the present invention, amino acid is introduced in modification agent while reductant reducing nano-silver, obtain the amino-acid modified finisher solution containing Nano Silver, the particle diameter of Nano Silver is generally less than 30nm, be applied to the modification of fiber or its fabric, fiber or its fabric face is made evenly to be fixed with the amino acid of Nano Silver and covalent cross-linking, shown in Fig. 2 is take lysine as the modification agent modification fabric of reductant, with the micro-structural of the covalent cross-linking of crosslinking agent and lysine between its cellulose fibre, make modified fiber or its fabric possess antibacterial and moisturizing simultaneously, lead wet, the multiple modified function of parent's skin skin-protection and health-care, change the technical problem that existing modification technology modified function is single, and have and adsorb set more by force with corpus fibrosum, the technological merit that its fastness to washing improves greatly, the anti-microbial property overcoming prior art existence is undesirable, the technical problem of fastness to washing difference, fabric after arrangement is after 50 washings, still all can more than 95% be reached to the bacteriostasis rate of Escherichia coli and staphylococcus aureus, the technical program also overcomes simultaneously and comprises cotton fiber, viscose acetal fibre, tencel fiber, Modal fibre, bamboo fibre, flax fibre or its fabric are in the easy wrinkle of interior existence, easy shrink, the technical problems such as dyestuff dye-uptake is undesirable, modified fiber or its fabric, crease-resistant, shrink, the technical performance indexs such as Dye up-take are all significantly improved and enhanced, creasy recovery angle improves more than 50 °, the dye-uptake of dyestuff improves more than 5%, more than 99% is reached to the bacteriostasis rate of Escherichia coli and staphylococcus aureus, make modification fabric health, comfortableness and the user demand more meeting affine human body or other organism attractive in appearance.Modification agent preparation method and method of modifying disclosed in the technical program have operation simplification, technique environmental protection, get close to the technological merit that nature is pollution-free, the used time is short, and process cost is low, added value of product is high.
Accompanying drawing explanation
Fig. 1 is dyeing curve map.
Fig. 2 is the microstate schematic diagram of crosslinking agent and amino acid and cellulose fibre covalent cross-linking, shown in the long curve of waveform is wherein cellulose fibre, by crosslinking agent B TCA and lysine LYS covalent cross-linking between the large molecule of two cellulose fibres, the stain between the large molecule of two cellulose fibres is the Nano Silver of evenly attachment.
Detailed description of the invention
To be described in detail the technology contents of the present patent application below by following examples.Wherein, also can replace cotton fiber in each embodiment or its fabric by viscose acetal fibre, tencel fiber, Modal fibre, bamboo fibre, flax fibre or its fabric, effect is identical; Described surfactant, also can be replaced the Tween80 in embodiment by Span-80, the JFC in similar, paregal O, effect is also identical.
embodiment 1
Step one, the agent of Preparation of amino acid Nano Silver modification:
The silver nitrate aqueous solution of silver solution to be mass concentration be 0.01g/L;
The equal miscible fluid of amino acid is the dispersed mixed solution of following component, comprise the amino acid solution that mass concentration is 20g/L, comprise the hexylene glycol glycidyl ether crosslinking agent that mass concentration is 20g/L, comprise the Tween-80 surfactant that mass concentration is 2g/L; For the consideration of cost aspect, amino acid solution can select the aqueous solution such as the more dominant lysine of cost performance, glutamic acid, methionine;
Silver solution and the equal miscible fluid of amino acid mix by the volume ratio of 1: 1, and under 95 DEG C of temperature conditions, mixing speed is not less than 200 revs/min, through 30 minutes, obtain the agent of amino acid nano-silver modification.
The modification method of step 2, cotton fiber or its fabric:
Cotton fiber or its fabric are immersed in the agent of amino acid nano-silver modification, its bath raio is 1: 30, rolls through two leachings two, and each dipping 15 minutes under room temperature, executing roll compacting power is 0.9kg/cm
2, liquid carrying rate is 70%, and it is placed in baking oven, in 40 DEG C of temperature preliminary dryings 5 minutes, then bakes 3 minutes in 80 DEG C of temperature, dries, obtain modification fabric after being washed to neutrality at 40 DEG C of temperature.
embodiment 2
Step one, the agent of Preparation of amino acid Nano Silver modification
The silver nitrate aqueous solution of silver solution to be mass concentration be 0.03g/L;
The equal miscible fluid of amino acid is the dispersed mixed solution of following component: comprise the amino acid solution that mass concentration is 40g/L, comprises the butanetetra-carboxylic acid crosslinking agent that mass concentration is 40g/L, comprises the Tween-80 surfactant that mass concentration is 4g/L.Wherein, for the consideration of cost aspect, amino acid solution can select the aqueous solution such as the more dominant lysine of cost performance, glutamic acid, methionine;
Silver solution and the equal miscible fluid of amino acid mix by the volume ratio of 1: 1, and be heated to 100 DEG C, strong stirring 30 minutes, its mixing speed is not less than 200 revs/min, obtain amino acid nano-silver modification liquid.
The modification method of step 2, cotton fiber or its fabric
Cotton fiber or its fabric are immersed in amino acid nano-silver modification liquid, its bath raio 1: 30, roll under room temperature through two leachings two, each dipping 15 minutes, draught pressure is 0.9kg/cm
2, liquid carrying rate is 70%, to put in baking oven 80 DEG C of preliminary dryings 5 minutes, then bakes 3 minutes at 160 DEG C of temperature, to be washed to after neutrality in 80 DEG C of oven dry, to obtain modification product.
embodiment 3
Step one, the agent of Preparation of amino acid Nano Silver modification
The silver nitrate aqueous solution of silver solution to be mass concentration be 0.05g/L;
The equal miscible fluid of amino acid is the dispersed mixed solution of following raw material: comprise the amino acid solution that mass concentration is 60g/L, comprises the butanetetra-carboxylic acid crosslinking agent that mass concentration is 60g/L, comprises the Tween-80 surfactant that mass concentration is 6g/L; Wherein for the consideration of cost aspect, amino acid solution can select the aqueous solution such as the more dominant lysine of cost performance, glutamic acid, methionine;
Silver solution and the equal miscible fluid of amino acid mix by the volume ratio of 1: 1, and under 95 DEG C of temperature conditions, mixing speed is not less than 200 revs/min, through 30 minutes, obtain the agent of amino acid nano-silver modification.
The modification method of step 2, cotton fiber or its fabric
Cotton fiber or its fabric are immersed in the agent of amino acid nano-silver modification, its bath raio 1: 30, roll under room temperature through two leachings two, each dipping 15 minutes, executing roll compacting power is 0.9kg/cm
2, liquid carrying rate is 70%, to put in baking oven 80 DEG C of preliminary dryings 5 minutes, then bake 3 minutes, after being washed to neutrality at 160 DEG C of temperature, dry at 80 DEG C of temperature.
Following table is detection tables of data that is dyed, crease-resistant to the modification fabric sample of above-described embodiment and antibacterial experiment,
.
Dyeability test is wherein:
Wherein the dyeing prescription of REACTIVE DYES is:
The red BF-3B 2%(o.w.f. of refined lattice element)
Soda ash Na
2cO
320g/L
Glauber salt Na
2sO
430g/L
Bath raio 30:1
Dye with the dyeing curve shown in Fig. 1, its washing post processing is: the soap flakes adding 3g/l, boils 5 minutes, airing after washing at the temperature of 95 DEG C, obtains testing sample.
Wrinkle resistance test wherein:
Select YG (B) 541E type Full automatic digital formula fabric crease elasticity test instrument.Method of testing: the crease resistance of fabric represents with creasy recovery angle.This experiment adopts the assay method pressing creasy recovery angle by GB/T 3819-1997, and the normal beam technique in " mensuration of textile fabric crease recovery replys horn cupping " measures.
Anti-microbial property test wherein: adopt GB GB/T20944.3-2008 " evaluation the 3rd part of antibacterial textile performance: concussion method " to test, test bacterial classification is gram-positive bacteria staphylococcus aureus and Gram-negative bacteria Escherichia coli.Sample bacteriostasis rate computing formula is as follows:
In formula: Y is bacteriostasis rate (%); Wb is the viable bacteria concentration (CFU/mL) after blank sample oscillating contact 18 h in flask; Wc is the viable bacteria concentration (CFU/mL) after fabric sample oscillating contact 18 h to be measured in flask.
Claims (8)
1. amino acid nano-silver modification agent, it is characterized in that the agent of this modification is mixed by 1:1 volume ratio by silver-colored solution and the equal miscible fluid of amino acid, obtained after stirring 30 ~ 45 minutes at 95 ~ 100 DEG C of temperature simultaneously, described silver-colored solution is the silver nitrate aqueous solution of 0.01 ~ 0.05g/L mass concentration scope, the equal miscible fluid of described amino acid is amino acid solution, the mixed solution that is uniformly dispersed of crosslinking agent and surfactant, the mass concentration of amino acid solution is wherein 20 ~ 60 g/L, crosslinking agent selects one of fatty alcohol glycidol ether or polybasic carboxylic acid, mass concentration is 20 ~ 60 g/L, surfactant is fatty alcohol-polyoxyethylene ether, its mass concentration is 2 ~ 6 g/L.
2. amino acid nano-silver modification according to claim 1 agent, is characterized in that described fatty alcohol glycidol ether is one of any in hexylene glycol glycidol ether, butanediol diglycidyl ether, propylene glycol diglycidylether, ethylene glycol diglycidylether.
3. amino acid nano-silver modification according to claim 1 agent, is characterized in that described polybasic carboxylic acid is one of any in BTCA, citric acid, poly.
4. amino acid nano-silver modification according to claim 1 agent, is characterized in that described surfactant is one of any in Span-80, Tween80, JFC, paregal O.
5. amino acid nano-silver modification according to claim 1 agent, it is characterized in that described amino acid solution be in lysine solution, glutamic acid aqueous solution or the methionine aqueous solution any one.
6. the preparation method of one of any described amino acid nano-silver modification agent in a claim 1 to 5, it is characterized in that the method is: the equal miscible fluid of amino acid mixes by 1:1 volume ratio with silver-colored solution, stir 30 ~ 45 minutes at 95 ~ 100 DEG C of temperature simultaneously, obtained, wherein, described silver-colored solution is the silver nitrate aqueous solution of 0.01 ~ 0.05g/L mass concentration scope, the equal miscible fluid of described amino acid is amino acid solution, the mixed solution that is uniformly dispersed of crosslinking agent and surfactant, the mass concentration of amino acid solution is wherein 20 ~ 60 g/L, crosslinking agent selects one of fatty alcohol glycidol ether or polybasic carboxylic acid, mass concentration is 20 ~ 60 g/L, surfactant is fatty alcohol-polyoxyethylene ether, its mass concentration is 2 ~ 6 g/L.
7. an application rights requires the modification fabric that in 1 to 5, one of any described amino acid nano-silver modification agent obtains, it is characterized in that this modification fabric obtains by the following method: corpus fibrosum or corpus fibrosum fabric immerse in the agent of amino acid nano-silver modification, its bath raio is 1: 30, roll through two leachings two, each dipping 15 minutes, liquid carrying rate was 70 ~ 90%, by preliminary drying in 40 ~ 80 DEG C of temperature 5 minutes, bake 3 minutes through 80 ~ 160 DEG C of temperature again, be washed to neutrality, oven dry.
8. modification fabric according to claim 7, is characterized in that described corpus fibrosum or corpus fibrosum fabric are cotton fiber, viscose acetal fibre, tencel fiber, Modal fibre, bamboo fibre, flax fibre or its fabric.
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Cited By (12)
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| CN105064008A (en) * | 2015-08-22 | 2015-11-18 | 赵兵 | Preparation method and application of nano-silver particles |
| CN105088755A (en) * | 2015-08-22 | 2015-11-25 | 赵兵 | Preparation method and application of silver nano-particles |
| CN105088753A (en) * | 2015-08-22 | 2015-11-25 | 赵兵 | Method for preparing nano-silver and nano-silver antibacterial cotton/linen/bamboo fiber blended fabric by tablet |
| CN105088754A (en) * | 2015-08-22 | 2015-11-25 | 赵兵 | Method for preparing nano-silver and nano-silver antibacterial fabric by honey |
| CN105133300A (en) * | 2015-08-22 | 2015-12-09 | 钱景 | Method for preparing nanosilver and finishing fabric |
| CN105133299A (en) * | 2015-08-22 | 2015-12-09 | 赵兵 | Method for preparing nanosilver from honey and finishing cotton linen bamboo fiber fabric |
| CN105177994A (en) * | 2015-09-25 | 2015-12-23 | 浙江德清恒锦时装有限公司 | Breathable and antibacterial cashmere sweater |
| CN109403026A (en) * | 2018-10-31 | 2019-03-01 | 嘉兴珠韵服装有限公司 | A kind of preparation method of dyeing and finishing technology pretreating reagent |
| CN112575409A (en) * | 2020-12-01 | 2021-03-30 | 江苏合源纺织科技有限公司 | Flame-retardant cotton-like polyester-nylon composite superfine fiber and production method thereof |
| CN112796105A (en) * | 2020-12-31 | 2021-05-14 | 砾维(新乡)纺织有限公司 | Production process of pure cotton CP flame-retardant fabric |
| CN115160453A (en) * | 2022-07-11 | 2022-10-11 | 东华大学 | Preparation method and application of biomolecule-based chelating film-forming agent |
| CN116556051A (en) * | 2023-05-19 | 2023-08-08 | 珠海厚洺服饰有限公司 | Antioxidation silver fiber fabric |
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| CN105064008A (en) * | 2015-08-22 | 2015-11-18 | 赵兵 | Preparation method and application of nano-silver particles |
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| CN105088753A (en) * | 2015-08-22 | 2015-11-25 | 赵兵 | Method for preparing nano-silver and nano-silver antibacterial cotton/linen/bamboo fiber blended fabric by tablet |
| CN105088754A (en) * | 2015-08-22 | 2015-11-25 | 赵兵 | Method for preparing nano-silver and nano-silver antibacterial fabric by honey |
| CN105133300A (en) * | 2015-08-22 | 2015-12-09 | 钱景 | Method for preparing nanosilver and finishing fabric |
| CN105133299A (en) * | 2015-08-22 | 2015-12-09 | 赵兵 | Method for preparing nanosilver from honey and finishing cotton linen bamboo fiber fabric |
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| CN105177994B (en) * | 2015-09-25 | 2017-06-06 | 浙江德清恒锦时装有限公司 | A kind of cashmere sweater of air-permeable anti-bacterial |
| CN109403026A (en) * | 2018-10-31 | 2019-03-01 | 嘉兴珠韵服装有限公司 | A kind of preparation method of dyeing and finishing technology pretreating reagent |
| CN112575409A (en) * | 2020-12-01 | 2021-03-30 | 江苏合源纺织科技有限公司 | Flame-retardant cotton-like polyester-nylon composite superfine fiber and production method thereof |
| CN112796105A (en) * | 2020-12-31 | 2021-05-14 | 砾维(新乡)纺织有限公司 | Production process of pure cotton CP flame-retardant fabric |
| CN115160453A (en) * | 2022-07-11 | 2022-10-11 | 东华大学 | Preparation method and application of biomolecule-based chelating film-forming agent |
| CN116556051A (en) * | 2023-05-19 | 2023-08-08 | 珠海厚洺服饰有限公司 | Antioxidation silver fiber fabric |
| CN116556051B (en) * | 2023-05-19 | 2024-05-24 | 银维康新材料科技(珠海)有限公司 | Antioxidation silver fiber fabric |
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