CN103371182A - Double-complexing nanosilver polymer liquid antibacterial agent and preparation method thereof - Google Patents
Double-complexing nanosilver polymer liquid antibacterial agent and preparation method thereof Download PDFInfo
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- CN103371182A CN103371182A CN201210109194XA CN201210109194A CN103371182A CN 103371182 A CN103371182 A CN 103371182A CN 201210109194X A CN201210109194X A CN 201210109194XA CN 201210109194 A CN201210109194 A CN 201210109194A CN 103371182 A CN103371182 A CN 103371182A
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Abstract
The invention relates to a double-complexing nanosilver polymer liquid antibacterial agent and a preparation method thereof. According to the method, with nanosilver double salt, polyvinyl alcohol and polyvinylpyrrolidone as a dispersant, a protector and a stable film-forming agent and with sea wave is used as a complexing and reducing agent, nanosilver fine particles with the grain size of 3-5 nanometers is prepared and completely dispersed in aqueous solution containing the protector. The neutral nanosilver polymer antibacterial agent which is small in grain size, uniform in distribution, colorless and transparent and good in stability is prepared by the method. The double-complexing nanosilver polymer liquid antibacterial agent provided by the invention has the advantages that (1) the double-complexing nanosilver polymer solution prepared by the method is full-transparent broad spectrum neutral antibacterial agent and has solid content concentration of 0.001-0.01mol/L, and nanosilver fine particles are narrow in size distribution in the nanosilver polymer material; (2) the antibacterial agent used can be directly blended and diluted by using common purified water or tap water; (3) the solution is good in thermal stability, and the nanosilver fine particles are strong in oxidation stain resistance at a high temperature under radiation and guidance of sunlight, rays and electromagnetic waves; and (4) in the preparation and production process of the material, no waste water, exhaust gases or pollutants which damage the environment are emitted.
Description
[technical field]
The present invention relates to the technical field of antibacterial agent, more particularly, is extremely preparation method of a kind of twice complexing Nano Silver aggressiveness liquid antibacterial agent.
[background technology]
The argentiferous liquid antibacterial agent is the inorganic dissolution type antibacterial agent of a class that utilizes sterilization that its metal ion has or bacteria resistance function to make, silver ion is one of minimum kind of minimum inhibitory concentration in all metal ions, and non-toxic, colorless, extremely be suitable for preparing antibacterial agent.But silver salt has very strong photosensitized reaction, runs into all very easily variable colors of light or long preservation, so that the part antibacterial agent can decompose gradually under photothermy and lose antibacterial effect, causes the antibacterial agent performance not reach the instructions for use of practical application area.In order to keep the intrinsic broad-spectrum antibacterial property energy of silver-containing antibacterial agent, increase Durability of antimicrobial effect, weather resisteant and stability, present technique have realized nano-silver ionic is carried out repeatedly complex protection and modification.Twice complexing Nano Silver aggressiveness antibacterial agent material is a kind of metal ion of new construction and the polymer of coordination ion, and being also referred to as is a kind of complicated complex ion body.
[summary of the invention]
The objective of the invention is to be to overcome present the deficiencies in the prior art, and extremely preparation method of a kind of twice complexing Nano Silver aggressiveness liquid antibacterial agent will be provided.
The objective of the invention is to realize by following technical scheme:
A kind of twice complexing Nano Silver aggressiveness liquid antibacterial agent be the preparation method extremely, and primary raw material is silver oxide, silver nitrate, and silver chlorate, the step of implementation is:
(1) the polyvinyl pyrrolidone polyglycol solution that silver nitrate is dissolved in certain percentage concentration disperses in the 60hz ultrasonic drilling machine, and the time is 15 minutes.(2) with common salt with deionized water dissolve by a certain percentage the configuration for subsequent use.(3) with sodium hydroxid with deionized water dissolve by a certain percentage the configuration for subsequent use.(4) (1) is slowly added (2), at room temperature stir while adding, time is after 10-20 minute (3) to be added the continuation stirring just to obtain the argentiferous sediment in 10 minutes through entering even of 60hz ultrasonic drilling machine dispersion behind the filtration washing, and the time is 30 minutes.(5) (4) are joined in the aqueous solution that contains the hypo mixing, at room temperature stir the translucent solution that 2～3 little the reaction times have obtained containing silver ion.Wherein, the mol ratio of silver nitrate and common salt is 1: 3.75.The mol ratio of silver nitrate and sodium hydroxid is 0.1: 1～0.5:.
The concentration of above-described polyglycol solution is 0.1～1%.Hypo mixing complex solution is comprised of thiosulfate and phosphate, and its mass ratio is 0.1: 0.5.Other joins the phosphate of secondary complexing and the mass ratio of thiosulfate is 0.5: 1～1: 1.Described thiosulfuric acid can be selected from potassium thiosulfate, wherein a kind of of sodium thiosulfate.
Described phosphate can select phosphoric acid one hydrogen to receive, and biphosphate is received, wherein a kind of of sodium hexametaphosphate, potassium dihydrogen phosphate.
The silver ion solution that (5) expection configuration is obtained under 25*c～30*c, at the uniform velocity add (6) stir proceeded complexing and reduction reaction in 4～6 hours until stirring reaction till the antibiotic liquid solution all transparent of argentiferous liquid state.
Twice complexing antiseptic solution of argentiferous of the invention process is a kind of colorless and odorless, and be nontoxic, and the liquid of non-stimulated all-transparent has the function of broad-spectrum antibacterial antiviral.
The liquid antiseptic solution of this argentiferous can be used as antibiotic, and antibacterial disinfectant is widely used in:
(1) can be applied in the Antimicrobial sanitation material, antimicrobial medical apparatus coating aspect.
(2) can be as the finishing agent at the textile fabric fabric, the additive aspect of antibiotic plastic, the aspects such as antibiotic paint.
The Disinfection Effect of the neutral Nano Silver aggressiveness of twice complexing of the present invention antibacterial agent detects and assesses by Ministry of Public Health's " disinfection technology standard ", the result shows, use the antibacterial agent of 100ppm content in the time of 10 minutes, to Escherichia coli, the killing rate of Staphylococcus aureus reaches 99.9%, the antibacterial agent of 100ppm content 10 minutes reaches 99.9% to the killing rate of Candida albicans.
The neutral Nano Silver aggressiveness of twice complexing of the present invention antibacterial agent LD50＞10000mg/kg, non-stimulated to skin, with each 20 of male and female small white mouses, they are carried out gavage test, this test take seven days as one group of phase, carry out altogether three after dates discovery small white mouse without intoxicating phenomenon, none death, and small white mouse carried out disposable stimulation test, to the eye conjunctiva of mouse, the integration of skin irritatin reaction is zero.By above test explanation, this antibacterial agent is nontoxic, and without the obvious stimulation reaction, and safety is reliable, illustrates that the neutral Nano Silver aggressiveness of twice complexing of the present invention antibacterial agent is the non-stimulated safe anti-biotic material of avirulence.
[specific implementation method]
Extremely preparation method's embodiment of a kind of twice complexing Nano Silver aggressiveness liquid antibacterial agent of the present invention below is provided.
Embodiment one
(1) AGNO3 that gets 0.029mol stirs and to dissolve in the 100ml deionized water, adds polyethylene glycol 1.5ml, enters the ultrasonic drilling machine of 60hz frequency after stirring, and carries out ultrasonic and disperses 15 minutes.
(2) NACL that gets 0.085mol stirs the deionized water of dissolving in 100ml.
(1) AGNO3 dispersion liquid is added in (2) while stirring, time is to add 0.01molNAOH 5ml after 10～15 minutes to stir 30 minutes, the polyvinylpyrrolidone 150ml that the living hypostasis of reaction washs adding 1% after filtration enters the 60hz ultrasonic and disperses two groups, and every group of time is 15 minutes.Obtaining argentiferous emulsion lucifuge deposits for subsequent use.
(4) preparation of complex silver aggressiveness solution is got the 10g sodium thiosulfate and is dissolved in the deionized water of 350ml.
(5) getting the 5g sodium hexametaphosphate is dissolved in the deionized water of 350ml, (5) are added miscible stirring in (4), (6) the argentiferous emulsion dispersion liquid that (3) is obtained slowly evenly adds in (5), stir while adding, for the time 1 hour, at room temperature continue afterwards to stir 4～6 hours, until reaction stirred is to all transparent.
The antiseptic solution that above-mentioned reaction obtains all-transparent complexing Nano Silver aggressiveness is 3000mg/L.
Embodiment two
(1) gets the AGNO3 of 0.0235mol, dissolve in the 100ml deionized water, add polyethylene glycol 1ml, enter into the ultrasonic drilling machine of 60hz frequency through stirring, carry out ultrasonic and disperseed 15 minutes.
(2) NACL that gets 0.068mol dissolves in the deionized water of 100ml
To add while stirring the NAOH solution 3ml of stirring adding 0.01mol after 15 minutes in (2) solution under (1) dispersion liquid room temperature,, stirred 30 minutes.The polyvinylpyrrolidone 150ml that the living hypostasis of reaction washs adding 1% after filtration enters the 60hz ultrasonic and disperses two groups, and every group of time is 15 minutes.Obtaining argentiferous emulsion lucifuge deposits for subsequent use.
Getting the 8g sodium thiosulfate is dissolved in the deionized water of 850ml.
Getting the 4g biphosphate receives to be dissolved in (4) and stirred 15 minutes.
The argentiferous emulsion dispersion liquid that (3) are obtained slowly evenly adds in (5), stir while adding, for the time 1 hour.At room temperature continue afterwards to stir 4～6 hours, until reaction stirred is transparent to all disperseing.
The antiseptic solution that above-mentioned reaction obtains all-transparent complexing Nano Silver aggressiveness is 2000mg/L.
The solution conduct of twice complexing Nano Silver aggressiveness of the present invention is in the antibacterial finishing agent of textile material, the washing fastness on the weaving material and the evaluation and test of antibacterial effect.
Experiment 1
Get three of destarch pure cotton cloths, be diluted to 100ppm with twice complexing Nano Silver of 3000ppm aggressiveness antibacterial liquid with water purification or running water, be weighed as respectively a, b, c, after three sample cloth are immersed in the antibiotic finishing solution, soaked 30 minutes, the rear part moisture content of extruding respectively cloth is so that three sample cloth are respectively d, e, f is so that after sloughing the moisture content oven dry, the silver content of three sample cloth is respectively 50ppm, 100ppm, 150ppm.
Experiment 2
According to antibiotic fabric sample decantation test method washing among the textile industry standard FZ/T73023-2006 of the People's Republic of China (PRC) 30 times～50 times, JIS-L1902 carries out the test of antibiotic rate with above-mentioned each cloth specimen, and its result is as shown in the table:
| Washing times | Wash 30 times | Wash 30 times | Wash 50 times | Wash 50 times |
| Sample cloth number | Escherichia coli | Staphylococcus aureus | Escherichia coli | Staphylococcus aureus |
| A sample cloth | 93.5％ | 95.5％ | 91.5％ | 93.5 |
| B sample cloth | 99.9％ | 99.9％ | 99.3％ | 99.1％ |
| C sample cloth | 99.9％ | 99.9％ | 99.9％ | 99.9％ |
| D sample cloth | 95.0％ | 96.5％ | 92.5％ | 93.5％ |
| E sample cloth | 99.9％ | 99.9％ | 99.2％ | 99.4％ |
| F sample cloth | 99.9％ | 99.9％ | 99.9％ | 99.9％ |
Can draw from the data analysis of top form, greater than 50ppm the time, the washable standard number of times of textile material antibacterial effect is greater than 50 times at the consumption that uses this antibacterial agent.Meet the requirement of the antibiotic fabric sample among the textile industry standard FZ/T73023-2006 of the People's Republic of China (PRC).
The above is preferred embodiment of the present invention, and for improvement and the modification in the art as under the prerequisite that does not break away from innovation thinking of the present invention, these improvement and modifying also should be considered within the scope of protection of the present invention.
Claims (4)
1. the preparation method of twice complexing Nano Silver aggressiveness liquid antibacterial agent is characterized in that specifically preparing each step and is:
(1) silver nitrate is dissolved in the aqueous solution of PVP(polyvinyl pyrrolidone) of certain percentage concentration, in the ultrasonic drilling machine of 60HZ frequency, disperse after 15-30 minute, in the situation of lucifuge, add respectively a certain proportion of common salt under the room temperature and sodium hydroxid stirs while adding 10-15 minute, obtained the sediment of argentiferous, enter after the washing after filtration and disperse even grain in the 60HZ ultrasonic drilling machine, the time is 30 minutes;
(2) mol ratio of silver nitrate and common salt is 1: 3.75, and the mol ratio of silver nitrate and sodium hydroxid is 0.1: 1-0.5: 1.The reactant that (1) is obtained joins in the aqueous solution that contains hypo mixing reduction complexing, at room temperature stirs while adding 2-3 hour, obtains containing the translucent solution of silver ion, and rear continuation is stirred 2～3 hours until the reaction solution all-transparent;
(3) concentration of above-described PVP(polyvinyl pyrrolidone) complex solution is 0.1-1%.Hypo mixing complex solution is comprised of thiosulfate and phosphate, and its mass ratio is 0.1: 0.5-1: 0.5.
2. the preparation method of a kind of twice complexing Nano Silver aggressiveness liquid antibacterial agent as claimed in claim 1; it is characterized in that in the described step (1), silver nitrate being dissolved in the aqueous solution of PVP(polyvinyl pyrrolidone) of certain proportion concentration; in 60HZ frequency ultrasonic wave machine, disperse the preparation method of protection and complexing.
3. the preparation method of a kind of twice complexing Nano Silver aggressiveness liquid antibacterial agent as claimed in claim 1, it is characterized in that in described (1) at room temperature adding respectively a certain proportion of common salt in the situation in lucifuge and sodium hydroxid stirs while adding 10-15 minute, enter the 60HZ ultrasonic drilling machine after the sediment that has obtained argentiferous washs after filtration and disperse even grain, the time be 30 minutes the preparation method.
4. a kind of twice complexing Nano Silver aggressiveness as claimed in claim 1 tucked in the preparation method of attitude antibacterial agent, it is characterized in that the concentration at PVP(polyvinyl pyrrolidone) complex solution described in the described step (3) is 0.1-1%, hypo mixing complex solution is selected from a kind of in potassium thiosulfate or the sodium thiosulfate by thiosulfate.Phosphate is selected from a kind of in receiving of sodium hexametaphosphate or biphosphate.Its mass ratio is 0.1: 0.5-1: 0.5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108716115A (en) * | 2018-05-28 | 2018-10-30 | 陆爱明 | Anti-bacterial fibre, preparation method and applications |
| CN113383787A (en) * | 2020-03-12 | 2021-09-14 | 上海沪正实业有限公司 | Multivalent silver composite nano antibacterial agent and preparation method thereof |
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| CN1500858A (en) * | 2002-11-15 | 2004-06-02 | 沈阳万象生物技术有限公司 | Health caring fancy soap and preparing method thereof |
| WO2009048556A1 (en) * | 2007-10-08 | 2009-04-16 | Johnson & Johnson Vision Care, Inc. | Methods for forming stabilized metal salt particles |
| CN101731272A (en) * | 2009-12-24 | 2010-06-16 | 中国人民解放军军事医学科学院基础医学研究所 | Method for preparing antibacterial nanometer silver colloid |
| CN101926363A (en) * | 2009-06-23 | 2010-12-29 | 上海六立纳米材料科技有限公司 | Method for preparing liquid antibacterial agent containing complex silver |
| CN102197826A (en) * | 2010-03-25 | 2011-09-28 | 上海亿金纳米科技有限公司 | Novel large-scale method for preparing alkalescent nano-silver solution |
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- 2012-04-13 CN CN201210109194XA patent/CN103371182A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1500858A (en) * | 2002-11-15 | 2004-06-02 | 沈阳万象生物技术有限公司 | Health caring fancy soap and preparing method thereof |
| WO2009048556A1 (en) * | 2007-10-08 | 2009-04-16 | Johnson & Johnson Vision Care, Inc. | Methods for forming stabilized metal salt particles |
| CN101926363A (en) * | 2009-06-23 | 2010-12-29 | 上海六立纳米材料科技有限公司 | Method for preparing liquid antibacterial agent containing complex silver |
| CN101731272A (en) * | 2009-12-24 | 2010-06-16 | 中国人民解放军军事医学科学院基础医学研究所 | Method for preparing antibacterial nanometer silver colloid |
| CN102197826A (en) * | 2010-03-25 | 2011-09-28 | 上海亿金纳米科技有限公司 | Novel large-scale method for preparing alkalescent nano-silver solution |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108716115A (en) * | 2018-05-28 | 2018-10-30 | 陆爱明 | Anti-bacterial fibre, preparation method and applications |
| CN108716115B (en) * | 2018-05-28 | 2021-07-09 | 扬州天富龙科技纤维有限公司 | Antibacterial fiber, preparation method and application thereof |
| CN113383787A (en) * | 2020-03-12 | 2021-09-14 | 上海沪正实业有限公司 | Multivalent silver composite nano antibacterial agent and preparation method thereof |
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