CN103858933A - Preparation method of color-change-resisting chitosan-silver compounded antibacterial agent - Google Patents
Preparation method of color-change-resisting chitosan-silver compounded antibacterial agent Download PDFInfo
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- CN103858933A CN103858933A CN201410011141.3A CN201410011141A CN103858933A CN 103858933 A CN103858933 A CN 103858933A CN 201410011141 A CN201410011141 A CN 201410011141A CN 103858933 A CN103858933 A CN 103858933A
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Abstract
The invention discloses a preparation method of a color-change-resisting chitosan-silver compounded antibacterial agent. The preparation method is characterized by comprising the following steps: step 1, preparing an acidic chitosan solution and filtering out insoluble substances from the solution to form the chitosan solution; step 2, adding a silver salt solution into the chitosan solution, fully stirring and uniformly mixing, then adding a reducing agent having the same mol ratio as the silver salt to reduce the silver salt into nanometer silver sol, and stirring; and step 3, dropwise adding a certain amount of a chloroauric acid solution into the nanometer silver sol, treating the nanometer silver through a replacement gold plating reaction, and continuing to stir to obtain the color-change-resisting chitosan-silver compounded antibacterial agent. Compared with the prior art, the antibacterial agent prepared by the method disclosed by the invention can be preserved for 3 months at room temperature without deterioration, is applicable to antisepsis of light-colored fabrics, dressings, packing materials and the like, has a quite good killing effect on various strains such as general colon bacillus and staphylococcus aureus, and also can be used for effectively resisting influences of color change on the whiteness and appearance of the fabrics.
Description
Technical field
The present invention relates to textile technology field, be specifically related to a kind of preparation method of anti-tarnish chitosan-Yin complex antimicrobials.
Background technology
Shitosan is as a kind of natural antibacterial material, its research and apply long-standing.It has been generally acknowledged that, the antibacterial activity of shitosan comes from amino contained in its molecule (NH2), and it can form positively charged NH3+ under acid condition, plays the effect of kill bacteria.But a large amount of research with facts have proved, simple chitosan finishing is difficult to meet the application aspect antibacterial fabric, this is limited by the factor such as surface amino groups quantity, chitosan molecule amount with its antibacterial activity on the one hand, on the other hand because its larger molecular weight usually can cause fabric feeling variation; In the time improving consumption, also can bring the problem of fabric jaundice variable color.
In order to improve anti-microbial property, modification and the complex process of shitosan receive widespread attention, but modification can not be avoided feel variation and discoloration problem, and modified technique is also comparatively complicated, and some also will use the chemical substance of certain toxicity.In comparison, composite simple and easy to do, but the selection of built agent is comparatively crucial.What obtain common concern is by composite to silver-series antibacterial agent and shitosan, has had some relevant Research Literatures and patent to deliver.Because silver is to carry out sterilizing by hereditary factor or the photocatalysis generation active oxygen radical of destruction bacterium, this makes it antibacterially have efficient, lasting and a broad spectrum activity, therefore all obtain application in a lot of fields such as medical treatment, clothes, become one of the most ripe and efficient antibacterial agent at present.But, because silver ion is easy to be combined with airborne oxygen, under illumination, can also be reduced into silver-colored simple substance, thereby show brownly, affect outward appearance and the anti-microbial property of fabric.Shitosan is composite with silver, amino in chitosan molecule can be used as the stabilizing agent of silver ion or Nano Silver, active hydroxyl can with the carboxyl generation esterification of surface of cotton fabric, strengthen silver-colored binding strength, improve Durability of antimicrobial effect, and the antibiotic property that itself has can also play auxiliary antibacterial action, thereby reach shell Synergistic antimicrobial effect.
The Fu Hongbin of Chengdu Textile higher junior college etc. has studied cotton fabrics Nano Silver/chitosan antibacterial finishing in " cotton fabrics Nano Silver/chitosan antibacterial finishing " literary composition, first carries out antibiotic finish with 50 ℃ of dippings of Nano Silver; Carry out subsequently chitosan finishing, its consumption is 20 g/L.This composite finishing has reduced the loss of Nano Silver, has suppressed fabric look and has become, and the fabric washing-resistant effect after arrangement is better, but Nano Silver and shitosan substep arrange, increased the complexity of technique, and chitosan dosage is higher, easily causes the comfortableness of fabric to decline.The Zhang Yufei of Zhejiang University etc. in " stability of chitosan nano silver solution and the application on antibiotic finish of the fabric " literary composition, adopt chemical method directly in chitosan solution reduction prepared the spherical nano-silver that particle diameter is less than 50nm, under the acting in conjunction of shitosan and Nano Silver, fabric has fabulous antibiotic property and antimicrobial long-acting.But not mentioned changing color of textile problem, and in antibacterial agent used, the addition of silver is very high, meeting weighted cloth metachromatism, this is very limited its practical application.The Lie group of University Of Qingdao is in Chinese patent " a kind of preparation method of anti-tarnish chitosan complex silver antibacterial agent " (application number 200610069365.5), a kind of silver salt that adds solubility in shitosan is disclosed, add cationic compound simultaneously, if the kinds of surface activating agents such as alkyl trimethyl ammonium salt, many alkyl dimethyls ammonium salt, organosilicon quaternary ammonium salt are as resistance toner, play the object that prevents the variable color of shitosan silver antibacterial agent.Because cationic surfactant has certain toxicity conventionally, health is formed to potential threat, also there is query in its washing fastness.In addition, this patent has been applied the soluble silver salt of high concentration, it is combined with oxygen or is deepened brown by photo-reduction in air is early to be confirmed by practice, and therefore, in fact this invention fastness effect in the time processing white or light fabric exists larger query.
Fabric look becomes not only affects its outward appearance, also can bring huge puzzlement to other processing such as the dyeing and finishings of fabric.Therefore the fastness problem that solves argentiferous chitosan antimicrobial agent seems very important, is also one of its practical application major defect that must overcome.
Summary of the invention
The present invention is directed to deficiency of the prior art, a kind of preparation method of anti-tarnish chitosan-Yin complex antimicrobials is provided.
In order to solve the problems of the technologies described above, the present invention is solved by following technical proposals: a kind of preparation method of anti-tarnish chitosan-Yin complex antimicrobials, it is characterized in that comprising the following steps: step 1: the acid solution of configuration shitosan, and form chitosan solution after filtering insoluble matter wherein; Step 2: add silver salt solution in the described chitosan solution of preparing in described step 1, be fully uniformly mixed, then add and the reductant of silver salt equimolar ratio, silver salt is reduced into nano silver colloidal sol, stir 1 ~ 2 hour; Step 3: drip a certain amount of gold chloride (HAuCl in the nano silver colloidal sol of preparing in described step 2
44H
2o) solution, carries out immersion gold plating reaction to Nano Silver, continues to stir 1 ~ 2 hour, obtains described anti-tarnish chitosan-Yin complex antimicrobials.
Specifically, the configuration step of the chitosan solution in above-mentioned steps 1 is: first in deionized water, add acid, stir, add afterwards shitosan, stirring and dissolving 2 hours, left standstill after 12 hours, suction filtration, removes insoluble matter wherein, obtains described chitosan solution.
As preferably, above-mentioned acid is the weak solution of citric acid or acetic acid, and its concentration is 10g/L to 70g/L.
As preferably, the described silver salt solution in above-mentioned steps 2 is liquor argenti nitratis ophthalmicus, and described reductant is sodium borohydride or potassium borohydride.
As preferably, in above-mentioned steps 3, Nano Silver to be carried out in the reaction of immersion gold plating, immersion gold plating amount is silver-colored mass fraction 3% ~ 8%, and in final described anti-tarnish chitosan-Yin complex antimicrobials, the concentration of gold-plated Nano Silver is 1ppm to 15ppm.
As preferably, in above-mentioned anti-tarnish chitosan-Yin complex antimicrobials, the molecular weight of shitosan is 10kDa to 100kDa, and concentration is 2g/L to 10g/L.
Compared with prior art, the invention has the beneficial effects as follows: the anti-tarnish chitosan-Yin complex antimicrobials finally obtaining is with lurid clear solution, can at room temperature preserve and never degenerate for 3 months, be applicable to the antibacterial of light fabric, dressing, packaging material etc., many bacterial classifications such as common Escherichia coli, staphylococcus aureus etc. are had to good killing effect, can effectively resist the impact of variable color on fabric whiteness and outward appearance simultaneously.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1.
In the deionized water of 90ml, add 1ml acetic acid (content >99.5%), stir, adding afterwards 1g molecular weight is the shitosan of 10kDa, stirring and dissolving 2 hours, leaves standstill after 12 hours suction filtration, remove insoluble matter wherein, obtain shitosan weak solution.In this solution, add prepare in advance 10
-3the liquor argenti nitratis ophthalmicus 3ml of mol/L, stirs and mixes for 5 minutes, adds gradually while stirring afterwards 10 of new preparation
-3the sodium borohydride solution 3ml of mol/L, is nano silver colloidal sol by silver nitrate reduction, continues to stir 2 hours, leaves standstill.In the solution of this shitosan-Nano Silver, splash into beforehand dilution to 10 afterwards
-5the HAuCl of mol/L
44H
2o solution 2ml, continues to stir 2 hours afterwards, obtains the nano silver colloidal sol of surface gold-plating 3%, then adds deionized water to 100ml, obtains anti-tarnish chitosan-Yin complex antimicrobials of the present invention, and its outward appearance is with lurid clear solution.After being encapsulated, place under room temperature, within 3 months, never degenerate, deposit-free generates.
With this antibacterial agent, the pure cotton cloth of bleaching is carried out to impregnation process, bath raio 1:40, temperature 50 C, dipping 30min, 100%, 75 ℃ of oven dry 10min of liquid carrying rate, rinsing, the rear test fabric whiteness of oven dry decline and are less than 3%.With the anti-microbial property of concussion method test cloth specimen, Escherichia coli, staphylococcus aureus are all reached to 100% sterilization rate.Fabric is placed nondiscolouring in 10 days in 55 ℃ of baking ovens.
Embodiment 2.
In the deionized water of 70ml, add 5g citric acid, stir, adding afterwards 0.5g molecular weight is the shitosan of 50kDa, and stirring and dissolving 2 hours left standstill after 12 hours, and suction filtration, removes insoluble matter wherein, obtains shitosan weak solution.In this solution, add prepare in advance 10
-3the liquor argenti nitratis ophthalmicus 10ml of mol/L, stirs and mixes for 5 minutes, adds gradually while stirring afterwards 10 of new preparation
-3the sodium borohydride solution 10ml of mol/L, is nano silver colloidal sol by silver nitrate reduction, continues to stir 1 hour, leaves standstill.In the solution of this shitosan-Nano Silver, splash into beforehand dilution to 10 afterwards
-5the HAuCl of mol/L
44H
2o solution 5.5ml, continues to stir 2 hours afterwards, obtains the nano silver colloidal sol of surface gold-plating 5%, then adds deionized water to 100ml, obtains of the present invention with lurid anti-tarnish chitosan-silver antibacterial agent clear solution.After being encapsulated, place under room temperature, within 3 months, never degenerate, deposit-free generates.
Embodiment 3.
In the deionized water of 60ml, add 4g citric acid, stir, adding afterwards 0.2g molecular weight is the shitosan of 100kDa, and stirring and dissolving 2 hours left standstill after 12 hours, and suction filtration, removes insoluble matter wherein, obtains shitosan weak solution.In this solution, add prepare in advance 10
-3the liquor argenti nitratis ophthalmicus 15ml of mol/L, stirs and mixes for 5 minutes, adds gradually while stirring afterwards 10 of new preparation
-3the sodium borohydride solution 15ml of mol/L, is nano silver colloidal sol by silver nitrate reduction, continues to stir 2 hours, leaves standstill.In the solution of this shitosan-Nano Silver, splash into beforehand dilution to 10 afterwards
-5the HAuCl of mol/L
44H
2o solution 8ml, continues to stir 1 hour afterwards, obtains the nano silver colloidal sol of surface gold-plating 5%, then adds deionized water to 100ml, obtains of the present invention with lurid anti-tarnish chitosan-silver antibacterial agent clear solution.After being encapsulated, place under room temperature, within 3 months, never degenerate, deposit-free generates.
Claims (6)
1. a preparation method for anti-tarnish chitosan-Yin complex antimicrobials, is characterized in that comprising the following steps: step 1: the acid solution of configuration shitosan, and form chitosan solution after filtering insoluble matter wherein; Step 2: add silver salt solution in the described chitosan solution of preparing in described step 1, be fully uniformly mixed, then add and the reductant of silver salt equimolar ratio, silver salt is reduced into nano silver colloidal sol, stir 1 ~ 2 hour; Step 3: drip a certain amount of gold chloride (HAuCl in the nano silver colloidal sol of preparing in described step 2
44H
2o) solution, carries out immersion gold plating reaction to Nano Silver, continues to stir 1 ~ 2 hour, obtains described anti-tarnish chitosan-Yin complex antimicrobials.
2. the preparation method of a kind of anti-tarnish chitosan-Yin complex antimicrobials according to claim 1, it is characterized in that: the configuration step of the chitosan solution in described step 1 is: first in deionized water, add acid, stir, add afterwards shitosan, stirring and dissolving 2 hours, leaves standstill after 12 hours suction filtration, remove insoluble matter wherein, obtain described chitosan solution.
3. the preparation method of a kind of anti-tarnish chitosan-Yin complex antimicrobials according to claim 2, is characterized in that: described acid is the weak solution of citric acid or acetic acid, and its concentration is 10g/L to 70g/L.
4. the preparation method of a kind of anti-tarnish chitosan-Yin complex antimicrobials according to claim 1, is characterized in that: the described silver salt solution in described step 2 is liquor argenti nitratis ophthalmicus, and described reductant is sodium borohydride or potassium borohydride.
5. according to the preparation method of a kind of anti-tarnish chitosan-Yin complex antimicrobials described in arbitrary claim in 1 to 4, it is characterized in that: in described step 3, Nano Silver is carried out in the reaction of immersion gold plating, immersion gold plating amount is 3% ~ 8% of silver-colored mass fraction, and in final described anti-tarnish chitosan-Yin complex antimicrobials, the concentration of gold-plated Nano Silver is 1ppm to 15ppm.
6. the preparation method of a kind of anti-tarnish chitosan-Yin complex antimicrobials according to claim 5, is characterized in that: in described anti-tarnish chitosan-Yin complex antimicrobials, the molecular weight of shitosan is 10kDa to 100kDa, and concentration is 2g/L to 10g/L.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105040418A (en) * | 2015-08-22 | 2015-11-11 | 苏州正业昌智能科技有限公司 | Manufacture method of nano-gold antibacterial blended fabric |
| CN105133349A (en) * | 2015-08-25 | 2015-12-09 | 无锡市长安曙光手套厂 | Antibacterial Lycra fabrics and preparation method thereof |
| CN106857658A (en) * | 2017-03-30 | 2017-06-20 | 安徽省银锂子生物科技发展有限公司 | It is a kind of carry with, the Nano Silver table-ware disinfection liquid of efficient quick sterilization |
| CN108835125A (en) * | 2018-08-10 | 2018-11-20 | 湖州大本营科技有限公司 | A kind of preparation method and applications of micro-nano silver/chitosan compound anti-bacteria agent |
| CN108902179A (en) * | 2018-08-10 | 2018-11-30 | 张家港市汇鼎新材料科技有限公司 | A kind of preparation method of silver-chitosan composite antibiotic material |
| CN109169706A (en) * | 2018-07-19 | 2019-01-11 | 大美泰康（天津）生态科技有限公司 | Complex antimicrobials and antibacterial bacteriostatic type multifunctional inorganic ecologic coating obtained |
| CN109235026A (en) * | 2018-08-23 | 2019-01-18 | 合肥普尔德医疗用品有限公司 | A kind of medical material preparation method based on antimicrobial nano silver chemical modification |
| CN110876386A (en) * | 2019-11-20 | 2020-03-13 | 厦门稀土材料研究所 | Rare earth oxide and nano-silver synergistic antibacterial agent and preparation method thereof |
| CN111168081A (en) * | 2020-01-20 | 2020-05-19 | 中车工业研究院有限公司 | Metal nanoparticle-cotton fiber composite fabric and preparation method and application thereof |
| CN112616853A (en) * | 2020-04-03 | 2021-04-09 | 祁海强 | Preparation method of high-dispersion anti-discoloration nano-silver antibacterial agent material |
| CN113172968A (en) * | 2021-05-31 | 2021-07-27 | 石狮市骏驰贸易有限公司 | Breathable anti-swelling silver film fabric |
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| JPH08268821A (en) * | 1995-04-03 | 1996-10-15 | Sangi Co Ltd | Antibacterial agent composition |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105040418A (en) * | 2015-08-22 | 2015-11-11 | 苏州正业昌智能科技有限公司 | Manufacture method of nano-gold antibacterial blended fabric |
| CN105133349A (en) * | 2015-08-25 | 2015-12-09 | 无锡市长安曙光手套厂 | Antibacterial Lycra fabrics and preparation method thereof |
| CN106857658A (en) * | 2017-03-30 | 2017-06-20 | 安徽省银锂子生物科技发展有限公司 | It is a kind of carry with, the Nano Silver table-ware disinfection liquid of efficient quick sterilization |
| CN109169706A (en) * | 2018-07-19 | 2019-01-11 | 大美泰康（天津）生态科技有限公司 | Complex antimicrobials and antibacterial bacteriostatic type multifunctional inorganic ecologic coating obtained |
| CN108835125A (en) * | 2018-08-10 | 2018-11-20 | 湖州大本营科技有限公司 | A kind of preparation method and applications of micro-nano silver/chitosan compound anti-bacteria agent |
| CN108902179A (en) * | 2018-08-10 | 2018-11-30 | 张家港市汇鼎新材料科技有限公司 | A kind of preparation method of silver-chitosan composite antibiotic material |
| CN109235026A (en) * | 2018-08-23 | 2019-01-18 | 合肥普尔德医疗用品有限公司 | A kind of medical material preparation method based on antimicrobial nano silver chemical modification |
| CN110876386A (en) * | 2019-11-20 | 2020-03-13 | 厦门稀土材料研究所 | Rare earth oxide and nano-silver synergistic antibacterial agent and preparation method thereof |
| CN110876386B (en) * | 2019-11-20 | 2022-01-14 | 厦门稀土材料研究所 | Rare earth oxide and nano-silver synergistic antibacterial agent and preparation method thereof |
| CN111168081A (en) * | 2020-01-20 | 2020-05-19 | 中车工业研究院有限公司 | Metal nanoparticle-cotton fiber composite fabric and preparation method and application thereof |
| CN112616853A (en) * | 2020-04-03 | 2021-04-09 | 祁海强 | Preparation method of high-dispersion anti-discoloration nano-silver antibacterial agent material |
| CN113172968A (en) * | 2021-05-31 | 2021-07-27 | 石狮市骏驰贸易有限公司 | Breathable anti-swelling silver film fabric |
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