CN101633045A - Nanometer silver collosol, preparation method and application thereof - Google Patents
Nanometer silver collosol, preparation method and application thereof Download PDFInfo
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- CN101633045A CN101633045A CN200910091031A CN200910091031A CN101633045A CN 101633045 A CN101633045 A CN 101633045A CN 200910091031 A CN200910091031 A CN 200910091031A CN 200910091031 A CN200910091031 A CN 200910091031A CN 101633045 A CN101633045 A CN 101633045A
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Abstract
The invention relates to a nanometer silver collosol, a preparation method and an application thereof. The preparation method comprising the following steps: dissolving reductor, alcohol and fatty alcohol in a closed reactor to prepare a mixed dispersion reductor solution; and then carrying out reaction between a silver salt alcohol solution and the mixed dispersion reductor solution for 6-72 hours under the temperature of 35-70 DEG C to obtain the nanometer silver collosol. The nanometer silver collosol has good antibacterial property and is very stable, safe in use and low in production cost, thereby being extensively used for the antibacterial processing of textiles and the antibacterial and deodorizing processing of shoes and having strong market competitiveness.
Description
[technical field]
The present invention relates to a kind of fibrous woven technical field.More specifically, the present invention relates to a kind of nano silver colloidal sol, also relate to the preparation method of described nano silver colloidal sol, relate to the purposes of described nano silver colloidal sol.
[background technology]
Nano Silver is a class wide spectrum, efficient, safe anti-biotic material, its preparation method generally is divided into physical method and chemical method two big classes: physical method need be used methods such as laser, electric arc high-frequency induction or electron beam irradiation, prepared Nano Silver purity height, particle diameter are controlled, but technical sophistication, equipment require high; Chemical method is with reduction silver ion and obtain Nano Silver, and is simple to operate, cost is lower, but granularity is not easy control, and product quality is often unstable.
Chinese patent CN 1583332A discloses a kind of nano silver colloidal sol and preparation method thereof: made by silver nitrate, water, reducing agent and protecting colloid.In aqueous systems, even the protection of protecting colloid is arranged, nano-Ag particles also is easy to reunite, and can cause the shelf stability of nano silver colloidal sol to descend, when the special higher or used reducing agent reducing power of concentration silver-colored in system is strong.
Chinese patent CN 1669914A discloses a kind of preparation method of nano silver colloidal sol: choose the system of silver nitrate aqueous solution and surfactant, by adjustment to obtain nano silver colloidal sol.Because this system is not used specific reducing agent, though silver sol is relatively stable, but most of silver ion is not reduced and forms monomer silver in the system, this part silver ion that is not reduced under alkali condition, have chlorion to exist or conditions such as illumination under, can finally be reduced to silver and reunion, and this process is not controlled, and this has just limited its application.
U.S. Pat 6979491 Antimicrobial yarn having nanosilver particlesand methods for manufacturing the same: this Nano Silver is made by the aqueous solution and reducing agent glucose, vitamin and the hydrazine hydrate of nitrate; because this Nano Silver does not have dispersant or protective agent, nano-Ag particles is easy to reunite.
U.S. Pat 20090104437 Scalable silver nano-particle colloid: this Nano Silver is made by the aqueous solution, borane reducing agent sodium hydride and the stabilizing agent natrium citricum of silver nitrate, the reducing power of sodium borohydride is very strong, and obtained nano-Ag particles is big.
At present, need a kind of nano silver colloidal sol of constant product quality all the time, need a kind of simple to operate, cost is lower, the granularity nano silver colloidal sol preparation method of control easily.For this reason, the inventor has finished the present invention finally through a large amount of tests.
[summary of the invention]
[technical problem that will solve]
The purpose of this invention is to provide a kind of nano silver colloidal sol.
Another object of the present invention provides the preparation method of described nano silver colloidal sol.
Another object of the present invention provides the purposes of described nano silver colloidal sol.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of nano silver colloidal sol, it is characterized in that the silver particles content of described colloidal sol is 20-20000ppm, described silver particles particle diameter is 0.5nm-40nm, described silver particles particle diameter at room temperature preserve 100 days constant.
Preferably, the silver particles content of described colloidal sol is 500-10000ppm, and described silver particles particle diameter is 0.5nm-30nm.
The present invention relates to a kind of preparation method of nano silver colloidal sol, it is characterized in that the step of this method is as follows:
A, mixing disperse the preparation of reductant solution
In closed reactor, in weight portion with 0.1-10 part one or more reducing agents, 40-75 part ethanol that are selected from glycogen, polyvinylpyrrolidone or glucose make described the mixing with the dissolving of 22-60 part fatty alcohol and disperse reductant solution;
The preparation of B, nano silver colloidal sol
Silver salt is dissolved in makes concentration 0.005-4.0 weight % silver salt ethanolic solution in the ethanol, then under stirring, lucifuge and airtight condition, described silver salt ethanolic solution is added to the described mixing that obtains in step (A) to be disperseed in the reductant solution, described silver salt weight is 0.8: 1.2 to 1.2: 0.8 with the described ratio that mixes dispersion reductant solution weight, under temperature 35-70 ℃, reacted 6-72 hour then, obtain described nano silver colloidal sol.
A preferred embodiment of the invention, described silver salt are a kind of silver salt that is selected from silver nitrate, silver acetate, silver citrate or silver tartrate.
According to another kind of preferred implementation of the present invention, described glucose is selected from β-D-glucose, alpha-D-glucose or their mixture.
According to another kind of preferred implementation of the present invention, described fatty alcohol is one or more fatty alcohols that are selected from ethylene glycol, propane diols, glycerine, butanediol, butantriol, n-amyl alcohol or n-hexyl alcohol.
According to another kind of preferred implementation of the present invention, described glycogen molecule amount is 1500000-5000000.
According to another kind of preferred implementation of the present invention, described polyvinylpyrrolidonemolecules molecules amount is 30000-90000.
With the purposes in the antibiotic post-finishing agent, the concentration that it is characterized in that being used for the nano silver colloidal sol of antibacterial fabric processing is preferably 50-100ppm to the nano silver colloidal sol that the present invention relates to the preparation of described nano silver colloidal sol or described method at fabric.
The present invention relates to the purposes of nano silver colloidal sol in the natural fiber antibacterial deodourizing is handled of described nano silver colloidal sol or described method preparation, it is characterized in that described nano silver colloidal sol to the minimal inhibitory concentration of Escherichia coli and staphylococcus aureus less than 30ppm.
Below the present invention will be described in more detail.
The present invention relates to a kind of nano silver colloidal sol, it is characterized in that the silver particles content of described colloidal sol is 20-20000ppm, described silver particles particle diameter is 0.5nm-40nm, described silver particles particle diameter at room temperature preserve 100 days constant.
Nano Silver has broad-spectrum antiseptic, can kill various pathogenic microorganisms, than the stronger bactericide of antibiotic, can directly kill 650 various bacteria rapidly, makes its forfeiture fertility; Permeability is strong, can promote wound healing, cell growth and damaged cell reparation; Antibiotic lasting, safety non-toxic does not have any IR to skin yet; Characteristics such as have no drug resistance.
Nano silver colloidal sol of the present invention adopts X-ray diffraction (XRD) and transmission electron microscope to characterize.
XRD uses D/max-rA to change target polycrystal X-ray diffractometer and analyzes (Japanese Rigaku produces), and its condition is as follows: copper target (Cu Ka), X ray wavelength 1.5406nm, sweep limits are that 10-90 °, sweep speed were 0.02 degree/second.Nano silver colloidal sol of the present invention dripped carry out X-ray diffraction analysis on slide, it the results are shown in accompanying drawing 1, and this is strivied for survival at the characteristic absorption peak of simple substance silver, shows that the micelle in the nano silver colloidal sol of the present invention is a silver granuel.
Tem study uses JEM-1200EX (Japanese JEOL produces), measures under operating voltage 160KV.Silver content is that the nano silver colloidal sol of the present invention of 100ppm has carried out the transmission electron microscope test, and it the results are shown in accompanying drawing 2.This result shows that the particle diameter of nano silver colloidal sol of the present invention is 1-20nm.
This sample has been carried out the transmission electron microscope test after preserving 60 days under 25 ℃, it the results are shown in accompanying drawing 3.This result shows that the particle diameter of nano silver colloidal sol of the present invention still is 1-20nm.
Simultaneously, also carry out preserving 100 days similar test, obtained essentially identical result.
This shows that nano silver colloidal sol of the present invention has extraordinary stability.
But this specification comparative example 1 result shows that the particle diameter of the nano silver colloidal sol of employing prior art for preparing distributes much wideer than the present invention, and its stability is also much lower.
Preferably, the silver particles content of colloidal sol of the present invention is 500-10000ppm, and described silver particles particle diameter is 0.5nm-30nm.
The present invention relates to a kind of preparation method of nano silver colloidal sol.
The preparation method's of this nano silver colloidal sol step is as follows:
A, mixing disperse the preparation of reductant solution
In closed reactor, in weight portion with 0.1-10 part one or more reducing agents, 40-75 part ethanol that are selected from glycogen, polyvinylpyrrolidone or glucose make described the mixing with the dissolving of 22-60 part fatty alcohol and disperse reductant solution.
Glycogen is a kind of polysaccharide of storing in animal and bacterial cell, is made up of glucose fully.Glycogen is white amorphous powder under drying regime, and odorless is pleasantly sweet.Show brownish red with Iod R, under 430-490nm, present maximum light absorption.Its water-soluble colloidal solution that forms is insoluble to ethanol.Its structure is similar to amylopectin, mainly is alpha-D-glucose.The glycogen that the present invention uses is a product sold on market at present, for example Shanghai continue bright and beautiful chemical Science and Technology Ltd. with trade name N632-2X product sold, Shanghai super grind bio tech ltd with trade name Glycogen Type II product sold or permanent big Parkson biology (Beijing) development in science and technology Co., Ltd with trade name 549-00161 product sold.
Preferably, described glycogen molecule amount is 1500000-5000000.
Polyvinylpyrrolidone white or off-white powder or particle have hygroscopicity, and odorless or little smelly, water-soluble, alkali, acid and polar organic solvent have very strong expansion character, have strong complexing power, also have good adhesive effect.
The polyvinylpyrrolidone that the present invention uses is a product sold on market at present, and for example Boai NKY Pharmaceutical Co., Ltd is with trade name
Dimension chemical industry Co., Ltd ties up ketone material Science and Technology Ltd. with trade name polyvinylpyrrolidone product sold with trade name PVP-K homopolymerization series product sold or Shanghai in PVP K product sold, Jiaozhuo.
Preferably, described polyvinylpyrrolidonemolecules molecules amount is 30000-90000.
The glucose that the present invention uses is distributed in nature monose the most widely.Glucose contains five hydroxyls, an aldehyde radical.This aldehyde radical has reproducibility, and these hydroxyls can esterification take place with acid.Natural glucose, no matter be dissociate or combination, all belong to the D configuration, in the aqueous solution, mainly exist with pyrans formula configuration ether ring, be the equilibrium mixture of α and two kinds of configurations of β.
In the present invention, described glucose is selected from β-D-glucose, alpha-D-glucose or their mixture.
β-D-glucose, the alpha-D-glucose that the present invention uses is product sold on market at present.
The glucose that the present invention uses is the mixture that β-D-glucose and alpha-D-glucose mix with any ratio, be natural glucose, for example Qingzhou City China health glucose Co., Ltd with trade name Dextrose Monohydrate product sold, Zouping timely snow DEXTROSE ANHYDROUS Co., Ltd with trade name DEXTROSE ANHYDROUS product sold or northization fine chemicals Co., Ltd with trade name glucose product sold.
In the present invention, described ethanol is product sold on market at present, for example is absolute ethyl alcohol or Different concentrations of alcohol aqueous products usually.
According to the present invention, described fatty alcohol can be unitary fatty alcohol, binary aliphatic alcohol or multi-alcohol.
Described unitary fatty alcohol for example is selected from the fatty alcohol of n-amyl alcohol or n-hexyl alcohol.
Described binary aliphatic alcohol for example is selected from the fatty alcohol of ethylene glycol, propane diols or butanediol.
Described ternary aliphatic alcohol for example is selected from the fatty alcohol of glycerine or butantriol.
In the present invention, described fatty alcohol all is a product sold on market at present.
In the present invention, described closed reactor should be appreciated that it is a kind ofly to disperse any reactor that can reach isolated with extraneous air in the reductant solution process in the described mixing of preparation, and purpose is to prevent glucose oxidase.Described closed reactor for example is Weihai Chemical Machinery Co., Ltd. with trade name enclosed reactor product sold, ocean, Zhengzhou metal structure Manufacturing Co., Ltd with trade name electrical heating stainless steel reaction pot or Wuxi Su Yang chemical equipment Co., Ltd with trade name electrical heating stainless steel cauldron product sold.
The preparation of B, nano silver colloidal sol
Silver salt is dissolved in makes concentration 0.005-4.0 weight % silver salt ethanolic solution in the ethanol, then under stirring, lucifuge and airtight condition, described silver salt ethanolic solution is added to the described mixing that obtains in step (A) to be disperseed in the reductant solution, described silver salt weight is 0.8: 1.2 to 1.2: 0.8 with the described ratio that mixes dispersion reductant solution weight, under temperature 35-70 ℃, reacted 6-72 hour then, obtain described nano silver colloidal sol.
According to the present invention, described silver salt is a kind of silver salt that is selected from silver nitrate, silver acetate, silver citrate or silver tartrate.
Preferably, described silver salt is a kind of silver salt that is selected from silver nitrate, silver acetate or silver tartrate.
More preferably, described silver salt is a kind of silver salt that is selected from silver nitrate or silver acetate.
Described silver salt is dissolved in makes the silver salt ethanolic solution in the ethanol.
The concentration of described silver salt ethanolic solution is 0.03-2.0 weight % preferably, more preferably is 0.1-1.7 weight %.
Then, the silver salt ethanolic solution that makes is added to the described mixing that obtains in step (A) to be disperseed in the reductant solution, described silver salt weight and the described ratio preferably 0.9: 1.1 to 1.1: 0.9 that disperses reductant solution weight that mixes more preferably are 0.95: 1.05 to 1.05: 0.95.
The described mixture that obtains reacted 6-72 hour under temperature 35-70 ℃, obtained described nano silver colloidal sol.Preferably, the described mixture that obtains reacted 8-36 hour under temperature 40-60 ℃.More preferably, the mixture that obtains reacted 8-12 hour under temperature 45-60 ℃.
The preparation of described nano silver colloidal sol is to carry out under stirring, lucifuge and airtight condition.
Described stirring is to use common dasher to stir, in the described nano silver colloidal sol process of preparation, its mixing speed is controlled at 40-1600 rev/min, be about to the blade linear velocity and be controlled at the 0.1-20 meter per second, cross low or too high blade linear velocity and do not help forming the silver granuel silver particles directly that meets the requirements.Certainly, also can use other agitator to stir, but need satisfy the requirement of its mixing speed.
Described lucifuge should be appreciated that it is the light that does not have natural daylight or any other light source in the described nano silver colloidal sol process of preparation, and purpose is to eliminate fully these light to forming the influence of fine silver particle.
Described airtight should be appreciated that is that the atmosphere and the reactor extraneous air of inside reactor do not have any exchange in the described nano silver colloidal sol process of preparation, and purpose is to prevent that air is to described reaction medium oxidation.
After reaction finished, the nano silver colloidal sol product that obtains adopted X-ray diffraction method (XRD) and transmission electron microscope to detect.
With the purposes in the antibiotic post-finishing agent, the concentration that it is characterized in that being used for the nano silver colloidal sol of antibacterial fabric processing is preferably 50-100ppm to the nano silver colloidal sol that the present invention relates to the preparation of above-mentioned nano silver colloidal sol or the method for the invention at fabric.
When using as fabric finishing agent, described nano silver colloidal sol using method is: with deionized water nano silver colloidal sol of the present invention is made work of treatment liquid, the concentration of Nano Silver can be controlled at 50-60ppm; Take padding method to handle described fabric then, for example silk and common gauze, making its fabric liquid carrying rate is 75-100%, keeps 0.5-2.0 hour, dries at temperature 80-100 ℃ again.
The present invention relates to the purposes of nano silver colloidal sol in the natural fiber antibacterial deodourizing is handled of described nano silver colloidal sol or described method preparation, it is characterized in that described nano silver colloidal sol to the minimal inhibitory concentration of Escherichia coli and staphylococcus aureus less than 30ppm.Described Escherichia coli for example are Escherichia coli ATCC 25922, and described staphylococcus aureus for example is staphylococcus aureus ATCC 6538.
Describe the nano silver colloidal sol that uses the present invention's preparation below in detail and handle the detection test.
1, detection method:
A, anti-microbial property testing standard
Antibacterial ring test (qualitative): GB/T 20944.1-2007 " the evaluation part 1 of antibacterial textile performance: agar diffusion method ".
Absorption process test (quantitatively): GB/T 20944.2-2007 " the evaluation part 2 of antibacterial textile performance: absorption process ", JIS L 1902-" test of 2002 textile fabrics antibacterial activities and efficient ", Ministry of Public Health's disinfection technology standard (version in 2002) 2.1.8.
B, fungicidal properties testing standard:
Fungicidal properties method of testing: ASTM G21-96 " the antimycotic mensuration of synthesized polymer material ".
C, decantation test
Decantation test is with reference to the washing procedure of FZ/T 73023-2006 " antibiosis knitting product appendix C antibiotic fabric sample decantation test method ".
2, testing result is as follows:
The relation of table 1 antibiotic silk sample washing times and inhibition zone diameter
Antibiotic property and mildew resistance after the antibiotic cotton gauze sample of table 2 washs 50 times
The above results clearly illustrates that, after using the nano silver colloidal sol processing natural fiber of the present invention's preparation, significantly do not reduce through inhibition zone diameters after 100 washings, still be higher than 90% through the bacteriostasis rate to Escherichia coli ATCC 25922 and staphylococcus aureus ATCC 6538 after 50 washings.
[beneficial effect]
The present invention has following beneficial effect:
Use equipment is few, and technology is simple, and is pollution-free, is convenient to suitability for industrialized production; The nano silver colloidal sol of the present invention preparation is safe to use, and anti-microbial property is good, and stability is splendid, through 100 washing backs the bacteriostasis rate of Escherichia coli and staphylococcus aureus still is higher than 90%, described silver particles particle diameter at room temperature preserve 100 days constant.The antibacterial and deodouring that can be applicable to antibacterial fabric processing and footwear is handled, and production cost is low, has the market competitiveness.
[Figure of description]
Fig. 1 is the X-ray diffractogram of nano silver colloidal sol of the present invention
Fig. 2 is the transmission electron microscope figure of nano silver colloidal sol of the present invention
Fig. 3 is that nano silver colloidal sol of the present invention is at the transmission electron microscope picture of placing after 60.
[specific embodiment]
Embodiment 1: the preparation of the nano silver colloidal sol of concentration 100ppm
Preparation process is as follows:
At first, in covering reactor, 1 part of glycogen, 40 parts of ethanol are made described the mixing with 59 parts of ethylene glycol dissolvings and disperseed reductant solution in weight portion.
Then, silver acetate is dissolved in makes concentration 0.017 weight % silver salt ethanolic solution in the ethanol, then under stirring, lucifuge and airtight condition, described silver salt ethanolic solution is added to the described mixing that obtains in front to be disperseed in the reductant solution, wherein said silver salt weight 50g, described mixing disperses reductant solution weight 50g, reacts 10 hours under 60 ℃ of temperature then, obtains described nano silver colloidal sol.
Adopt the X-ray diffraction method of describing in this specification to obtain result shown in Figure 1, show that the micelle in the nano silver colloidal sol of the present invention is a silver granuel.Adopt the tem study of describing in this specification to determine that the particle diameter of nano silver particles is 1-20nm.
After using the nano silver colloidal sol processing natural fiber of this embodiment preparation, adopt the method for describing in this specification to detect, significantly not reducing through inhibition zone diameters after 100 washings, is respectively 98.2% and 97.9% through the bacteriostasis rate to Escherichia coli ATCC 25922 and staphylococcus aureus ATCC 6538 after 50 washings.
Embodiment 2: the preparation of the nano silver colloidal sol of concentration 50ppm
Preparation process is as follows:
The embodiment of this embodiment is identical with embodiment's 1, but uses 0.1 part of glucose, 75 parts of ethanol and 24.9 parts of ethylene glycol;
Then, silver nitrate is dissolved in makes concentration 0.0085 weight % silver nitrate ethanolic solution in the ethanol, then under stirring, lucifuge and airtight condition, described silver nitrate ethanolic solution is added to the described mixing that obtains in front to be disperseed in the reductant solution, wherein said silver nitrate weight 50g, described mixing disperses reductant solution weight 50g, reacts 12 hours under 50 ℃ of temperature then, obtains described nano silver colloidal sol.
Adopt same detection method to detect, what its result and embodiment 1 obtained comes to the same thing.
Adopting the method for describing in this specification to detect, significantly do not reduce through inhibition zone diameters after 100 washings, is respectively 99.2% and 98.4% through the bacteriostasis rate to Escherichia coli ATCC 25922 and staphylococcus aureus ATCC 6538 after 50 washings.
Embodiment 3: the preparation of the nano silver colloidal sol of concentration 200ppm
Preparation process is as follows:
The embodiment of this embodiment is identical with embodiment's 1, but uses 5 weight account polyethylene pyrrolidones, 55 parts by weight of ethanol, 40 weight portion glycerine.
Then, silver acetate is dissolved in makes concentration 0.034 weight % silver nitrate ethanolic solution in the ethanol, then under stirring, lucifuge and airtight condition, described silver acetate ethanolic solution is added to the described mixing that obtains in front to be disperseed in the reductant solution, wherein said silver acetate weight 50g, described mixing disperses reductant solution weight 50g, reacts 25 hours under 50 ℃ of temperature then, obtains described nano silver colloidal sol.
Adopt same detection method to detect, what its result and embodiment 1 obtained comes to the same thing.
Adopting the method for describing in this specification to detect, significantly do not reduce through inhibition zone diameters after 100 washings, is respectively 97.2% and 99.4% through the bacteriostasis rate to Escherichia coli ATCC 25922 and staphylococcus aureus ATCC 6538 after 50 washings.
Embodiment 4: the preparation of the nano silver colloidal sol of concentration 2000ppm
Preparation process is as follows:
The embodiment of this embodiment is identical with embodiment's 1, but uses 1 weight portion glucose, 8 weight account polyethylene pyrrolidones, 60 parts by weight of ethanol and 31 weight portion glycerine
Then, silver nitrate is dissolved in makes concentration 0.34 weight % silver nitrate ethanolic solution in the ethanol, then under stirring, lucifuge and airtight condition, described silver nitrate ethanolic solution is added to the described mixing that obtains in front to be disperseed in the reductant solution, wherein said silver nitrate weight 50g, described mixing disperses reductant solution weight 50g, reacts 50 hours under 50 ℃ of temperature then, obtains described nano silver colloidal sol.
Adopt same detection method to detect, what its result and embodiment 1 obtained comes to the same thing.
Adopting the method for describing in this specification to detect, significantly do not reduce through inhibition zone diameters after 100 washings, is respectively 99.0% and 98.6% through the bacteriostasis rate to Escherichia coli ATCC 25922 and staphylococcus aureus ATCC 6538 after 50 washings.
Embodiment 5: the preparation of the nano silver colloidal sol of concentration 5000ppm
Preparation process is as follows:
The embodiment of this embodiment is identical with embodiment's 1, but uses 2 weight portion glucose, 8 weight account polyethylene pyrrolidones, 50 parts by weight of ethanol and 40 weight portion n-amyl alcohols.
Then, silver nitrate is dissolved in makes concentration 0.85 weight % silver nitrate ethanolic solution in the ethanol, then under stirring, lucifuge and airtight condition, described silver nitrate ethanolic solution is added to the described mixing that obtains in front to be disperseed in the reductant solution, wherein said silver nitrate weight 50g, described mixing disperses reductant solution weight 50g, reacts 70 hours under 40 ℃ of temperature then, obtains described nano silver colloidal sol.
Adopt similarly to Example 1 that detection method detects, its result shows that the micelle in the nano silver colloidal sol of the present invention is a silver granuel.Adopt the tem study of describing in this specification to determine that the particle diameter of nano silver particles is 10-35nm.
Adopting the method for describing in this specification to detect, significantly do not reduce through inhibition zone diameters after 100 washings, is respectively 99.1% and 98.9% through the bacteriostasis rate to Escherichia coli ATCC 25922 and staphylococcus aureus ATCC 6538 after 50 washings.
Embodiment 6: the preparation of the nano silver colloidal sol of concentration 10000ppm
Preparation process is as follows:
The embodiment of this embodiment is identical with embodiment's 1, but uses 3 weight portion glycogens, 9 weight account polyethylene pyrrolidones, 40 parts by weight of ethanol and 48 weight portion propane diols.
Then, silver nitrate is dissolved in makes concentration 1.7 weight % silver nitrate ethanolic solutions in the ethanol, then under stirring, lucifuge and airtight condition, described silver nitrate ethanolic solution is added to the described mixing that obtains in front to be disperseed in the reductant solution, wherein said silver nitrate weight 50g, described mixing disperses reductant solution weight 50g, reacts 65 hours under 45 ℃ of temperature then, obtains described nano silver colloidal sol.
Adopt similarly to Example 1 that detection method detects, its result shows that the micelle in the nano silver colloidal sol of the present invention is a silver granuel.Adopt the tem study of describing in this specification to determine that the particle diameter of nano silver particles is 16-38nm.
Adopting the method for describing in this specification to detect, significantly do not reduce through inhibition zone diameters after 100 washings, is respectively 99.6% and 99.2% through the bacteriostasis rate to Escherichia coli ATCC 25922 and staphylococcus aureus ATCC 6538 after 50 washings.
Embodiment 7: the preparation of the nano silver colloidal sol of concentration 20000ppm
Preparation process is as follows:
The embodiment of this embodiment is identical with embodiment's 1, but uses 3 weight portion glucose, 9 weight account polyethylene pyrrolidones, 40 parts by weight of ethanol and 48 weight portion propane diols.
Then, silver nitrate is dissolved in makes concentration 3.4 weight % silver nitrate ethanolic solutions in the ethanol, then under stirring, lucifuge and airtight condition, described silver nitrate ethanolic solution is added to the described mixing that obtains in front to be disperseed in the reductant solution, wherein said silver nitrate weight 50g, described mixing disperses reductant solution weight 50g, reacts 18 hours under 45 ℃ of temperature then, obtains described nano silver colloidal sol.
Adopt similarly to Example 1 that detection method detects, its result shows that the micelle in the nano silver colloidal sol of the present invention is a silver granuel.Adopt the tem study of describing in this specification to determine that the particle diameter of nano silver particles is 12-30nm.
Adopting the method for describing in this specification to detect, significantly do not reduce through inhibition zone diameters after 100 washings, is respectively 98.6% and 97.2% through the bacteriostasis rate to Escherichia coli ATCC 25922 and staphylococcus aureus ATCC 6538 after 50 washings.
The comparative example 1
Adopt embodiment two preparation nano-class silver colloidal solutions among the Chinese patent CN1876293A.
Adopt the tem study of describing in this specification to determine that the particle diameter of nano silver particles is 10～80nm, place that the particle diameter of nano silver particles is 60-140nm after 14 days.
Adopting the method for describing in this specification to detect, is respectively 68.1% and 57.4% through the bacteriostasis rate to Escherichia coli ATCC 25922 and staphylococcus aureus ATCC 6538 after 20 washings.
The comparative example 2
Adopt embodiment two preparation nano-class silver colloidal solutions among the Chinese patent CN101091991A.
Adopt the tem study of describing in this specification to determine that the particle diameter of nano silver particles is 1～10nm.
Adopting the method for describing in this specification to detect, is respectively 48.6% and 67.8% through the bacteriostasis rate to Escherichia coli ATCC 25922 and staphylococcus aureus ATCC 6538 after 50 washings.
The comparative example 3:
Adopt embodiment one preparation nano-class silver colloidal solution among the Chinese patent CN1669914A.
Adopt the tem study of describing in this specification to determine that the particle diameter of nano silver particles is 1～20nm.
Adopting the method for describing in this specification to detect, is respectively 92.1% and 93.4% through the bacteriostasis rate to Escherichia coli ATCC 25922 and staphylococcus aureus ATCC 6538 after 50 washings.But the white cotton of handling through this nano silver colloidal sol 6 hours was obvious variable color in indoor placement through natural lighting, and place March at indoor natural light through the handled white cotton cloth of the nano silver colloidal sol sample of all embodiment preparations of this specification, perusal is less than any change color.
The comparative example 4:
Adopt the method for describing in the specification to prepare antibacterial cotton cloth sample and detection simultaneously to the ProductName textiles antibacterial finishing agent JDFKS-001 of the big nanosecond science and technology in Shanxi, Xiamen Co., Ltd, Shanghai WeiLai New Materials Science Co., Ltd's product nano-silver antibacterial finishing agent T200-TA8-3 by name and the embodiment of the invention 5, estimate as follows:
Table 3 antibacterial cotton cloth is to the antibacterial effect of Escherichia coli ATCC25922
Table 4 antibacterial cotton cloth is to the antibacterial effect of staphylococcus aureus ATCC26538
The comparative example 5:
With the ProductName textiles antibacterial finishing agent JDFKS-001 of the big nanosecond science and technology in Shanxi, Xiamen Co., Ltd, the Shanghai WeiLai New Materials Science Co., Ltd's product nano-silver antibacterial finishing agent T200-TA8-3 by name and the embodiment of the invention 5 are as footwear antibiotic finish spray, handle shoe-pad simultaneously by the merchandise provided name A01220DordorHorse of Dr. Health Footcare International (Beijing) Co., Ltd., technology is as follows: get antibacterial finishing agent and join in 100 ml deionized water for 1 milliliter and make antimicrobial spray, adopt BeiJing ZhongKe's two provider of ring Science and Technology Ltd. product motor-driven high-pressure sprayers of AS-33 by name that shoe-pad is sprayed, to average every shoe-pad, contain antimicrobial spray 3g, shady naturally doing.Adopt in this specification antibiotic detection method to estimate it to the oidiomycetic antibacterial effect of white, result such as following table:
Table 5 antibacterial insoles is to the oidiomycetic antibacterial effect of white
Claims (10)
1, a kind of nano silver colloidal sol is characterized in that the silver particles content of described colloidal sol is 20-20000ppm, and described silver particles particle diameter is 0.5nm-40nm, described silver particles particle diameter at room temperature preserve 100 days constant.
2, nano silver colloidal sol according to claim 1 is characterized in that the silver particles content of described colloidal sol is 500-10000ppm, and described silver particles particle diameter is 0.5nm-30nm.
3, a kind of preparation method of nano silver colloidal sol is characterized in that the step of this method is as follows:
A, mixing disperse the preparation of reductant solution
In closed reactor, in weight portion with 0.1-10 part one or more reducing agents, 40-75 part ethanol that are selected from glycogen, polyvinylpyrrolidone or glucose make described the mixing with the dissolving of 22-60 part fatty alcohol and disperse reductant solution;
The preparation of B, nano silver colloidal sol
Silver salt is dissolved in makes concentration 0.005-4.0 weight % silver salt ethanolic solution in the ethanol, then under stirring, lucifuge and airtight condition, described silver salt ethanolic solution is added to the described mixing that obtains in step (A) to be disperseed in the reductant solution, described silver salt weight is 0.8: 1.2 to 1.2: 0.8 with the described ratio that mixes dispersion reductant solution weight, under temperature 35-70 ℃, reacted 6-72 hour then, obtain described nano silver colloidal sol.
4, method according to claim 3 is characterized in that described silver salt is a kind of silver salt that is selected from silver nitrate, silver acetate, silver citrate or silver tartrate.
5,, it is characterized in that described glucose is selected from β-D-glucose, alpha-D-glucose or their mixture according to the preparation method of the described nano silver colloidal sol of claim 3.
6, method according to claim 3 is characterized in that described fatty alcohol is one or more fatty alcohols that are selected from ethylene glycol, propane diols, glycerine, butanediol, butantriol, n-amyl alcohol or n-hexyl alcohol.
7,, it is characterized in that described glycogen molecule amount is 1500000-5000000 according to the preparation method of the described nano silver colloidal sol of claim 3.
8,, it is characterized in that described polyvinylpyrrolidonemolecules molecules amount is 30000-90000 according to the preparation method of the described nano silver colloidal sol of claim 3.
9, nano silver colloidal sol according to claim 1 and 2 or according to the nano silver colloidal sol of the described method of arbitrary claim among claim 3-8 preparation at fabric with the purposes in the antibiotic post-finishing agent, the concentration that it is characterized in that being used for the nano silver colloidal sol of antibacterial fabric processing is preferably 50-100ppm.
10, nano silver colloidal sol according to claim 1 and 2 or according to the purposes of nano silver colloidal sol in the natural fiber antibacterial deodourizing is handled of the described method of arbitrary claim among claim 3-8 preparation, it is characterized in that described nano silver colloidal sol to the minimal inhibitory concentration of Escherichia coli and staphylococcus aureus less than 30ppm.
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