CN103008683A - Preparation method for high-efficient monomer silver solution as well as high-efficient monomer silver gel and lotion - Google Patents
Preparation method for high-efficient monomer silver solution as well as high-efficient monomer silver gel and lotion Download PDFInfo
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Abstract
The invention provides a preparation method for high-efficient monomer silver solution. The preparation method comprises the following steps: aqueous solution of silver source compound is mixed with aqueous solution containing protective agent, and then mixed with aqueous solution of reducing agent, and the high-efficient monomer silver solution is obtained through reaction under the condition of stirring; and the stirring speed is 50 r/min-150 r/min, the reaction temperature is minus 5 DEG C to 10 DEG, and the reaction time is 30 min-200 min. According to the invention, the aqueous solution of silver source compound is mixed uniformly with the aqueous solution containing protective agent, so that silver ions are dispersed uniformly, then the aqueous solution of silver source compound is mixed with the aqueous solution of reducing agent, so that the silver ions can be quickly restored into silver atoms, the whole reaction process is carried out at a relatively low temperature, the high-efficient monomer silver prepared has uniform particle diameter, uniform distribution, and good stability, and the reaction time is within 30 min-200 min.
Description
Technical field
The present invention relates to field of medicaments, relate in particular to a kind of preparation method and efficient monomer silver gel and efficient monomer silver washing lotion of efficient monomer silver solution.
Background technology
Silver as antiseptic have nontoxic, without irritated, have no drug resistance and the multiple advantage such as has a broad antifungal spectrum, it only kills pathogen, do not injure normal cell, it has powerful bactericidal action to pathogenic bacteria of drug-resistant, staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Candida albicans, chlamydia trachomatis and gonococcus etc., can also repair impaired epithelial cell simultaneously.Illustrated in " about the survey report of silver-colored toxicity " that U.S. public health bureau nineteen ninety announces silver to human body without obvious toxic-side effects, local application, silver content is few, is safest application method.Continuous progress along with science and technology, people have obtained than the little a lot of efficient monomer silver in common silver granuel footpath, and its particle diameter is between 20 ~ 59nm, because it has larger specific area, so its sterilizing ability is stronger than traditional silver antibacterial agent, and the more little more even bactericidal effect of particle diameter is stronger.
At present, the preparation method of efficient monomer silver has a lot, mainly comprises physical method, chemical method and biological reducing method.Wherein physical method mainly contains sputter plating, mechanical ball-milling method and laser burn method, the physical method principle is simple, the product of preparation has higher purity, but it is had relatively high expectations to instrument and equipment, and producing cost is expensive, can only be used for the not high industrialization preparations of the size of efficient monomer silver particles and character requirement.Chemical method mainly contains micro emulsion method, sol-gel process, galvanoplastic, liquid phase chemical reduction method, photoreduction method etc., but it is higher that these methods have a cost, preparation process is complicated, unstable product quality, silver ion reacts incomplete shortcoming, simultaneously, can not guarantee that precipitation does not appear in efficient monomer silver in the process of depositing, therefore not yet realize the large-scale production of efficient monomer silver.
Wherein, chemical reduction method is the method for the present efficient monomer silver of preparation of commonly using, efficient monomer silver particle for fear of preparation in the preparation process is reunited, often need to add dispersant and protective agent, Zhang Zongtao etc. are take PVP as macromolecule dispersant, take hydrazine hydrate as reducing agent, having prepared average grain diameter in the aqueous solution is the ball shape silver powder of 30 ~ 100nm, and the result shows, higher reaction temperature is conducive to form little crystal grain silver powder (East China University of Science's journal, 1995,21:423 ~ 427), still, in the method, higher temperature can make nano silver colloidal sol produce the grey black precipitation, even produces silver mirror, has greatly affected purity and the productive rate of product; Wei Chunping is take sodium borohydride as reducing agent, and under the protection of polyvinylpyrrolidone, room temperature reduction liquor argenti nitratis ophthalmicus has synthesized Silver nanoparticles (Liaoning chemical industry; 2010; 7:697 ~ 699), but the Silver nanoparticles of the method preparation more easily reunites, and stable bad.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method and efficient monomer silver gel and efficient monomer silver washing lotion of efficient monomer silver solution, and the efficient monomer silver granuel footpath homogeneous of preparation is evenly distributed, and has good stability.
The invention provides a kind of preparation method of efficient monomer silver solution, comprising:
With the aqueous solution of silver-colored source compound with contain protectant aqueous solution, with the aqueous solution of reducing agent, react under the condition of stirring again, obtain efficient monomer silver solution;
Wherein, the speed of described stirring is 50r/min ~ 150r/min, and the temperature of described reaction is-5 ℃ ~ 10 ℃, and the time of described reaction is 30min ~ 200min.
Preferably, the mass ratio of described silver-colored source compound, protective agent and reducing agent is 1:(1 ~ 10): (0.05 ~ 0.5).
Preferably, the speed of described stirring is 90r/min ~ 110r/min.
Preferably, the temperature of described reaction is 0 ℃ ~ 5 ℃, and the time of described reaction is 150min ~ 180min.
Preferably, in the aqueous solution of described silver-colored source compound, the concentration of silver ion is 3.5g/L ~ 7.0g/L.
Preferably, described silver-colored source compound is selected from silver nitrate or silver ammonia complex.
Preferably, described protective agent is selected from any one or a few in polyvinyl alcohol, polyvinylpyrrolidone, gelatin, monohydric alcohol, polyalcohol, sorbierite, aromatic alcohol wax and the polynary arene; Described reducing agent is selected from sodium borohydride, H
2O
2, in formaldehyde, hydrazine hydrate, trisodium citrate, ascorbic acid, citric acid, ethanol, sugar, organic amine, polyalcohol and the ferrous salt any one or a few.
The present invention also provides a kind of efficient monomer silver solution of according to the method described above preparation.
The present invention also provides a kind of efficient monomer silver gel, is mixed by efficient monomer silver solution and assistant agent, and described efficient monomer silver solution is above-mentioned efficient monomer silver solution, and in the described efficient monomer silver gel, silver content is 200ppm ~ 500ppm.
The present invention also provides a kind of efficient monomer silver washing lotion, is mixed by efficient monomer silver solution and water, and described efficient monomer silver solution is above-mentioned efficient monomer silver solution, and in the described efficient monomer silver washing lotion, silver content is 50ppm ~ 300ppm.
The present invention by with the aqueous solution of silver-colored source compound with contain protectant aqueous solution; again with the aqueous solution of reducing agent; speed with 50r/min ~ 150r/min stirs, and reacts 30min ~ 200min under-5 ℃ ~ 10 ℃ the temperature, obtains efficient monomer silver solution.The present invention is at first with the aqueous solution of silver-colored source compound with to contain protectant aqueous solution even; silver ion is uniformly dispersed; again with the aqueous solution of reducing agent; make silver ion be reduced into rapidly silver atoms; whole course of reaction is all carried out at a lower temperature, and the efficient monomer silver granuel footpath homogeneous of preparation is evenly distributed; and have good stability, and 30min ~ 200min can finish reaction.
Description of drawings
Fig. 1 is that the efficient monomer silver solution of the embodiment of the invention 1 preparation amplifies 200000 times scanning electron microscope (SEM) photograph;
Fig. 2 is that the efficient monomer silver solution of the embodiment of the invention 1 preparation amplifies 30000 times scanning electron microscope (SEM) photograph;
Fig. 3 is that the efficient monomer silver solution of the embodiment of the invention 1 preparation is placed 30 days scanning electron microscope (SEM) photograph;
Fig. 4 is that the efficient monomer silver solution of the embodiment of the invention 3 preparations amplifies 50000 times scanning electron microscope (SEM) photograph;
Fig. 5 is that the efficient monomer silver solution of the embodiment of the invention 3 preparations is placed 30 days scanning electron microscope (SEM) photograph;
Fig. 6 is that the Nano silver solution of comparative example 1 preparation of the present invention amplifies 200000 times scanning electron microscope (SEM) photograph;
Fig. 7 is that the Nano silver solution of comparative example 1 preparation of the present invention amplifies 30000 times scanning electron microscope (SEM) photograph;
Fig. 8 is that the Nano silver solution of comparative example 1 preparation of the present invention is placed 30 days scanning electron microscope (SEM) photograph.
The specific embodiment
The invention provides a kind of preparation method of efficient monomer silver solution, may further comprise the steps:
With the aqueous solution of silver-colored source compound with contain protectant aqueous solution, with the aqueous solution of reducing agent, react under the condition of stirring again, obtain efficient monomer silver solution;
Wherein, the speed of described stirring is 50r/min ~ 150r/min, and the temperature of described reaction is-5 ℃ ~ 10 ℃, and the time of described reaction is 30min ~ 200min.
The present invention is at first with the aqueous solution of silver-colored source compound with to contain protectant aqueous solution even; silver ion is uniformly dispersed; again with the aqueous solution of reducing agent; make silver ion be reduced into rapidly silver atoms; whole course of reaction is all carried out at a lower temperature, and the efficient monomer silver granuel footpath homogeneous of preparation is evenly distributed; and have good stability, and 30min ~ 200min can finish reaction.
The present invention at first with the aqueous solution of silver-colored source compound with contain protectant aqueous solution.The aqueous solution of described silver-colored source compound obtains for silver-colored source compound is dissolved in the water.Described silver-colored source compound is preferably silver nitrate or silver ammonia complex, more preferably silver nitrate; Described silver ammonia complex is for containing Ag (NO
3)
2 +The compound of ion, the present invention is to the described Ag (NO that contains
3)
2 +The anion of the compound of ion there is no specific (special) requirements, is preferably OH
-, Cl
-And NO
3 -In any one or a few, OH more preferably
-The present invention there is no specific (special) requirements to the source of described silver-colored source compound, can be for generally commercially available.The present invention preferably adopts the mode of stirring that silver-colored source compound is dissolved in the water, and the speed of described stirring is preferably 50r/min ~ 150r/min, more preferably 90r/min～110r/min; The temperature of described stirring is preferably-5 ℃ ~ 10 ℃, more preferably 0 ℃ ~ 5 ℃; The time of described stirring is preferably 40min ~ 200min, more preferably 60min ~ 120min.In the aqueous solution of the silver-colored source compound that obtains, the concentration of silver ion is preferably 3.5g/L ~ 7.0g/L, more preferably 4.0g/L ~ 5.2g/L.Described protectant aqueous solution obtains for protective agent is dissolved in the water; Described protective agent is preferably any one or a few in polyvinyl alcohol, polyvinylpyrrolidone, gelatin, monohydric alcohol, polyalcohol, sorbierite, aromatic alcohol wax and the polynary arene, more preferably polyvinyl alcohol or polyvinylpyrrolidone; The present invention there is no specific (special) requirements to described protectant source, can be for generally commercially available; The present invention preferably adopts the mode of stirring that protective agent is dissolved in the water, and the speed of described stirring is preferably 50r/min～150r/min, more preferably 90r/min～110r/min; The temperature of described stirring is preferably-5 ℃ ~ 10 ℃, more preferably 0 ℃ ~ 5 ℃; The time of described stirring is preferably 40min ~ 200min, more preferably 60min～120min.What obtain contains in protectant aqueous solution, and protectant concentration is preferably 25g/L ~ 65g/L, more preferably 35g/L ~ 50g/L.
With the aqueous solution of silver-colored source compound with contain protectant aqueous solution after, the present invention preferably adopts the mode of stirring to make mixing more even, the speed of described stirring is preferably 50r/min～150r/min, more preferably 90r/min～110r/min; The temperature of described stirring is preferably-5 ℃ ~ 10 ℃, more preferably 0 ℃ ~ 5 ℃; The time of described stirring is preferably 40min ~ 200min, more preferably 80min～160min.
With the aqueous solution of silver-colored source compound with contain protectant aqueous solution after, with the aqueous solution of reducing agent, react under the condition of stirring again, can obtain efficient monomer silver solution.Described reducing agent is preferably sodium borohydride, H
2O
2, in formaldehyde, hydrazine hydrate, trisodium citrate, ascorbic acid, citric acid, ethanol, sugar, organic amine, polyalcohol and the ferrous salt any one or a few, more preferably sodium borohydride or trisodium citrate; The present invention there is no specific (special) requirements to the source of described reducing agent, can be for generally commercially available; In the aqueous solution of described reducing agent, the concentration of reducing agent is preferably 0.5g/L ~ 1.3g/L, more preferably 0.8g/L～1.1g/L.The speed of described stirring is preferably 50r/min ~ 150r/min, and more preferably 90r/min～110r/min most preferably is 100r/min ~ 105r/min; The temperature of described reaction is preferably-5 ℃ ~ 10 ℃, more preferably 0 ℃ ~ 5 ℃, most preferably is 2 ℃ ~ 4 ℃; The time of described reaction is preferably 30min ~ 200min, and more preferably 150min ~ 180min most preferably is 160min ~ 170min.Among the present invention, the mass ratio of described silver-colored source compound, protective agent and reducing agent is preferably 1:(1 ~ 10): (0.05 ~ 0.5), more preferably 1:(3 ~ 7): (0.1 ~ 0.3).
The present invention is at first with the aqueous solution of silver-colored source compound with to contain protectant aqueous solution even, thereby silver ion is uniformly dispersed, with the aqueous solution of reducing agent, makes silver ion be reduced into rapidly silver atoms again, whole course of reaction is all carried out at a lower temperature, when having avoided excess Temperature, because the Brownian movement aggravation, so that the interparticle collision chance increases, cause particle agglomeration, the grey black precipitation occurs, even produce silver mirror, thereby affect the shortcoming of product purity and productive rate; By reducing reaction temperature, the Brownian movement speed of control molecule, atom reduces collision, thereby reach stable reaction, make preparation the big or small homogeneous in efficient monomer silver granuel footpath, be evenly distributed, simultaneously, finish in the short period of time again reaction, overcome temperature and crossed the excessively slow deficiency of low reaction speed.
After obtaining efficient monomer silver solution, by SEM its pattern and stability are detected, the result shows, efficient monomer silver solution uniform particle diameter provided by the invention, be evenly distributed, and have good stability, in the efficient monomer silver solution that obtains, the particle diameter of silver atoms is preferably 20nm ~ 50nm, more preferably 30nm ~ 40nm; Its silver content is preferably 500ppm ~ 1500ppm, more preferably 700ppm ~ 1200ppm; Its solution colour is preferably brownish red.
The present invention also provides a kind of efficient monomer silver solution of according to the method described above preparation, and in the described efficient monomer silver solution, the particle diameter of silver atoms is preferably 20nm ~ 50nm, more preferably 30nm ~ 40nm; Its silver content is preferably 500ppm ~ 1500ppm, more preferably 700ppm ~ 1200ppm; Its solution colour is preferably brownish red.
The present invention also provides a kind of efficient monomer silver gel, mixed by efficient monomer silver solution and assistant agent, described efficient monomer silver solution is the efficient monomer silver solution of according to the method described above preparation, in the described efficient monomer silver gel, its silver content is preferably 200ppm ~ 500ppm, more preferably 250ppm ~ 400ppm; Preferably, described efficient monomer silver solution accounts for the 10wt% ~ 90wt% of described efficient monomer silver solution and assistant agent.The present invention there is no specific (special) requirements to the kind of described assistant agent, can be preparation gel well known to those skilled in the art assistant agent commonly used, and the present invention is preferably Acritamer 940, sodium hydroxide solution, ethylparaben ethanolic solution, glycerine solution and the aqueous solution.The present invention there is no specific (special) requirements to source and the purity of described Acritamer 940, sodium hydroxide solution, ethylparaben ethanolic solution, glycerine solution and the aqueous solution, can be for generally commercially available, and its purity can be technical grade.
Preferably, efficient monomer silver solution and Acritamer 940, sodium hydroxide solution, ethylparaben ethanolic solution, glycerine solution and aqueous solution that the present invention will prepare prepare efficient monomer silver gel; The ratio of the volume of the volume of the volume of described efficient monomer silver solution and the quality of Acritamer 940 and sodium hydroxide solution, the volume of ethylparaben ethanolic solution, glycerine solution and the volume of the aqueous solution is preferably 1mL:(0.01g ~ 0.03g): (0.005mL ~ 0.02mL): (0.005mL ~ 0.02mL): (0.1mL ~ 0.4mL): (1mL ~ 4mL); The mass concentration of described NaOH is preferably 20% ~ 60%; In the described efficient monomer silver solution, silver content is preferably 500ppm ~ 1500ppm.The present invention there is no specific (special) requirements to the order by merging of described efficient monomer silver solution and Acritamer 940, sodium hydroxide solution, ethylparaben ethanolic solution, glycerine solution and the aqueous solution, is preferably Acritamer 940, sodium hydroxide solution, ethylparaben ethanolic solution, glycerine solution, the aqueous solution and efficient monomer silver solution are sequentially added into.
The present invention also provides a kind of efficient monomer silver washing lotion, mixed by efficient monomer silver solution and water, described efficient monomer silver solution is the efficient monomer silver solution of according to the method described above preparation, in the described efficient monomer silver washing lotion, its silver content is preferably 50ppm ~ 300ppm, more preferably 100ppm ~ 200ppm; The volume ratio of described efficient monomer silver solution and water is preferably 1:1 ~ 15, more preferably 1:4 ~ 10.
Concrete, after the efficient monomer silver solution with water dilution with preparation, prepare efficient monomer silver washing lotion.
Efficient monomer silver gel and the efficient monomer silver washing lotion of preparation are used for clinical antibacterial tests, the result shows, efficient monomer silver gel provided by the invention and efficient monomer silver washing lotion can effectively be treated all kinds of vaginitis, prostatitis and acute and chronic rhinitis, can obviously improve symptom, and have no adverse reaction, product safety is effective.
The present invention is by being dissolved in the water silver-colored source compound and protective agent respectively and stirring; obtain respectively the aqueous solution of silver ion and contain protectant aqueous solution; again with the two mixing; again with the aqueous solution of reducing agent; speed with 50r/min ~ 150r/min stirs; react 30min ~ 200min under-5 ℃ ~ 10 ℃ the temperature, obtain efficient monomer silver solution.The present invention at first aqueous solution and the protectant aqueous solution with silver-colored source compound is even; silver ion is uniformly dispersed; again with the aqueous solution of reducing agent; make silver ion be reduced into rapidly silver atoms; whole course of reaction is all carried out at a lower temperature, and the efficient monomer silver granuel footpath homogeneous of preparation is evenly distributed; and have good stability, and 30min ~ 200min can finish reaction.
In order to further specify the present invention, below in conjunction with embodiment preparation method and the efficient monomer silver gel of efficient monomer silver solution provided by the invention are described in detail with efficient monomer silver washing lotion.
Embodiment 1
The 5g silver nitrate added in 1000mL2 ℃ the distilled water, stir 60min with the speed of 100r/min it is fully dissolved, obtain liquor argenti nitratis ophthalmicus; Simultaneously the 25g polyvinyl alcohol is added in 500mL2 ℃ the distilled water, stir 60min with the speed of 100r/min it is fully dissolved, obtain poly-vinyl alcohol solution; The liquor argenti nitratis ophthalmicus and the poly-vinyl alcohol solution that obtain are fully mixed, and under 2 ℃ the temperature, the speed stirring 120min with 100r/min obtains mixed solution; Then in the distilled water with 100mL2 ℃ of 0.085g sodium borohydride adding, speed stirring 60min with 100r/min fully dissolves it, and slowly join in the mixed solution of silver nitrate and polyvinyl alcohol, under 2 ℃ the temperature, speed with 100r/min stirs 180min, obtains efficient monomer silver solution.
With SEM the silver-colored solution of the efficient monomer of preparation being carried out pattern detects, testing result is seen Fig. 1 and Fig. 2, Fig. 1 is that the efficient monomer silver solution of the embodiment of the invention 1 preparation amplifies 200000 times scanning electron microscope (SEM) photograph, and Fig. 2 is that the efficient monomer silver solution of the embodiment of the invention 1 preparation amplifies 30000 times scanning electron microscope (SEM) photograph; By Fig. 1 and Fig. 2 as can be known, in the efficient monomer silver solution provided by the invention, the silver atoms that contains is of a size of about 20nm, and is evenly distributed.
The efficient monomer silver solution normal temperature lucifuge of preparation was placed 30 days, then by SEM its pattern is checked, thereby detect its stability.Experimental result is seen Fig. 3, Fig. 3 is that the efficient monomer silver solution of the embodiment of the invention 1 preparation is placed 30 days scanning electron microscope (SEM) photograph, and as shown in Figure 3, the efficient monomer silver solution of the present invention's preparation has good stability, its room temperature lucifuge was placed after 30 days, still was evenly to distribute.
Embodiment 2
The 4.0g silver nitrate added in 1000mL5 ℃ the distilled water, stir 60min with the speed of 100r/min it is fully dissolved, obtain liquor argenti nitratis ophthalmicus; Simultaneously the 20g polyvinyl alcohol is added in 500mL5 ℃ the distilled water, stir 60min with the speed of 100r/min it is fully dissolved, obtain poly-vinyl alcohol solution; The liquor argenti nitratis ophthalmicus and the poly-vinyl alcohol solution that obtain are fully mixed, and under 5 ℃ the temperature, the speed stirring 120min with 100r/min obtains mixed solution; Then in the distilled water with 100mL5 ℃ of 0.065g sodium borohydride adding, speed stirring 60min with 100r/min fully dissolves it, and slowly join in the mixed solution of silver nitrate and polyvinyl alcohol, under 5 ℃ the temperature, speed with 100r/min stirs 180min, obtains efficient monomer silver solution.
With SEM the silver-colored solution of the efficient monomer of preparation is carried out pattern and detect, the result shows that in the efficient monomer silver solution of present embodiment preparation, the silver atoms that contains is of a size of about 20nm, and is evenly distributed.
The efficient monomer silver solution normal temperature lucifuge of preparation was placed 30 days, then by SEM its pattern is checked, thereby detect its stability, experimental result shows, the efficient monomer silver solution of present embodiment preparation has good stability, its room temperature lucifuge was placed after 30 days, still was evenly to distribute.
Embodiment 3
The 5.0g silver nitrate added in 1000mL4 ℃ the distilled water, stir 120min with the speed of 100r/min it is fully dissolved, obtain liquor argenti nitratis ophthalmicus; Simultaneously the 18g polyvinylpyrrolidone is added in 500mL4 ℃ the distilled water, stir 120min with the speed of 100r/min it is fully dissolved, obtain polyvinylpyrrolidonesolution solution; The liquor argenti nitratis ophthalmicus and the polyvinylpyrrolidonesolution solution that obtain are fully mixed, and under 4 ℃ the temperature, the speed stirring 120min with 100r/min obtains mixed solution; Then in the distilled water with 100mL4 ℃ of 0.065g trisodium citrate adding, speed stirring 120min with 150r/min fully dissolves it, and slowly join in the mixed solution of silver nitrate and polyvinylpyrrolidone, under 4 ℃ the temperature, speed with 150r/min stirs 180min, obtains efficient monomer silver solution.
With SEM the silver-colored solution of the efficient monomer of preparation is carried out pattern and detect, testing result is seen Fig. 4, and Fig. 4 is that the efficient monomer silver solution of the embodiment of the invention 3 preparations amplifies 50000 times scanning electron microscope (SEM) photograph; As shown in Figure 4, in the efficient monomer silver solution that present embodiment provides, the silver atoms that contains is of a size of about 20nm, and is evenly distributed.
The efficient monomer silver solution normal temperature lucifuge of preparation was placed 30 days, then by SEM its pattern is checked, thereby detect its stability.Experimental result is seen Fig. 5, Fig. 5 is that the efficient monomer silver solution of the embodiment of the invention 3 preparations is placed 30 days scanning electron microscope (SEM) photograph, and as shown in Figure 5, the efficient monomer silver solution of the present invention's preparation has good stability, its room temperature lucifuge was placed after 30 days, still was evenly to distribute.
Comparative example 1
In beaker, add the 0.0449g polyvinylpyrrolidone, add stirring and dissolving under 20 ℃ of conditions of 30mL deionized water, again to the silver nitrate aqueous solution that wherein adds 5mL0.006mol/L, stir, then the concentration that dropwise adds the new configuration of 10mL in the reaction system is the sodium borohydride aqueous solution of 0.008mol/L, be stirred to solution by the colourless yellow that becomes, obtain Nano silver solution.
With SEM the Nano silver solution for preparing being carried out pattern detects, testing result is seen Fig. 6 and Fig. 7, Fig. 6 is that the Nano silver solution of comparative example 1 preparation of the present invention amplifies 200000 times scanning electron microscope (SEM) photograph, and Fig. 7 is that the Nano silver solution of comparative example 1 preparation of the present invention amplifies 30000 times scanning electron microscope (SEM) photograph; By Fig. 6 and Fig. 7 as can be known, in the Nano silver solution of comparative example preparation of the present invention, the silver atoms that contains is of a size of 50nm ~ 100nm, and agglomeration is arranged.
The Nano silver solution normal temperature lucifuge of preparation was placed 30 days, then by SEM its pattern is checked, thereby detect its stability.Experimental result is seen Fig. 8, Fig. 8 is that the Nano silver solution of comparative example 1 preparation of the present invention is placed 30 days scanning electron microscope (SEM) photograph, as shown in Figure 8, and the Nano silver solution less stable of comparative example preparation of the present invention, its room temperature lucifuge was placed after 30 days, and comparatively significantly agglomeration is arranged.
Embodiment 4
Bacterium stripping property test method by regulation in " the disposable use amenities sanitary standard " of version in 2002, the efficient monomer silver solution of embodiment 1 preparation, the efficient monomer silver solution of embodiment 3 preparations and the Nano silver solution of comparative example 1 preparation are carried out bacteriostatic test, the results are shown in Table 1, table 1 is the bacteriostatic test result of efficient monomer silver solution and the Nano silver solution that comparative example 1 prepares of the embodiment of the invention 1, embodiment 3 preparations.
The bacteriostatic test result of the efficient monomer silver solution of table 1 embodiment of the invention 1, embodiment 3 preparations and the Nano silver solution of comparative example 1 preparation
Embodiment 5
Be that the efficient monomer silver solution of 40% sodium hydroxide solution, 10mL ethylparaben ethanolic solution, 250mL glycerine solution, the 2500mL aqueous solution and 1000mL embodiment 1 preparation is sequentially added into and is prepared into gel in the reactor with 20g Acritamer 940,10mL concentration, can is in delivery device, prepare efficient monomer silver gel, wherein silver content is 350ppm.
Embodiment 6
The efficient monomer silver solution 100mL of embodiment 1 preparation is added the dilution of 900mL water, and then can prepares efficient monomer silver washing lotion in delivery device, and wherein silver content is 100ppm.
Embodiment 7
Be that the efficient monomer silver solution of 40% sodium hydroxide solution, 8mL ethylparaben ethanolic solution, 200mL glycerine solution, the 2000mL aqueous solution and 1000mL embodiment 3 preparations is sequentially added into and is prepared into gel in the reactor with 16g Acritamer 940,8mL concentration, can is in delivery device, prepare efficient monomer silver gel, wherein silver content is 350ppm.
Embodiment 8
The efficient monomer silver gel of research embodiment 5 preparation is to the result for the treatment of of various vaginitis and cervicitis:
Case load:
Selection suffers from patient each 72 examples, totally 216 examples of bacterial vaginosis BV, VVC and cervicitis.
The selection of case:
1. age l8～65 years old, the women;
2. the diagnostic criteria that meets bacterial vaginosis BV, VVC (vulvovaginal candidiasis), cervicitis;
3. voluntary participation clinical testing, and signature Informed Consent Form.
The case exclusion standard:
1. age＜18 year old or age＞65 year old;
2. merge the primary disease persons such as conscience kidney or hemopoietic system, the mental patient;
3. pregnancy or women breast-feeding their children;
4. allergic constitution or to the known composition allergy sufferers of this product;
5. the anti-inflammatory drug treatment was used in medication in front 1 week;
6. carried out other clinical testing person in 1 week;
7. the researcher thinks and should not carry out clinical testing person;
8. do not meet diagnostic criteria person;
9. the women (virgin) who has sexual intercourse is not arranged.
The clinical testing method:
Adopt open to test from the clinic trial as contrast;
Patients with Bacterial Vaginosis: the patient injects the vagina deep with the efficient monomer silver gel product of embodiment 5 preparations, and 1 of every day, every 3g is used in conjunction 7 days;
VVC (vulvovaginal candidiasis): the patient injects the vagina deep with the efficient monomer silver gel of embodiment 5 preparations, and 1 of every day, every 3g is used in conjunction 7 days;
Virus in patients with cervicitis: the patient injects the vagina deep with the efficient monomer silver gel of embodiment 5 preparations, and 1 of every day, every 3g is used in conjunction 9 days;
Drug withdrawal was followed up a case by regular visits to after 7 days, if the menstrual period then follows up a case by regular visits to after finishing menstrual period.
The clinical evaluation standard:
Recovery from illness: symptom and sign disappear substantially after the medication, and integrated value reduces 〉=90%;
Produce effects: cardinal symptom, sign are obviously improved after the medication, and integrated value reduces 〉=70%;
Effectively: cardinal symptom, sign are improved after the medication, and integrated value reduces 〉=30%;
Invalid: cardinal symptom and sign are without obvious improvement after the medication, and integrated value reduces＜30%.
Clinical test results:
1, case performance
The case performance of table 2 embodiment of the invention 8 gathers
| The sick kind | Enter to organize number | Finish number | Number comes off |
| Bacterial vaginosis BV | 72 | 69 | 3 |
| VVC | 72 | 68 | 4 |
| Cervicitis | 72 | 68 | 4 |
2, result of the test
The result of the test of table 3 embodiment of the invention 8 gathers
Result of the test shows: total obvious effective rate of efficient monomer silver gel treatment bacterial vaginosis BV provided by the invention is 62.32%, total effective rate is 89.86%, total obvious effective rate for the treatment of VVC is 57.35%, total effective rate is 91.18%, total obvious effective rate for the treatment of cervicitis is 57.35%, and total effective rate is 88.24%, can improve the symptoms such as itch, abnormal leucorrhea, private parts peculiar smell of its initiation, and bad reaction does not occur in process of the test, prove that this product is safe and effective.
Embodiment 9
The efficient monomer silver gel of research embodiment 5 preparation is to the result for the treatment of of chronic prostatitis:
Case load:
Select patients with chronic prostatitis totally 72 examples.
The selection of case:
1. age l8～65 years old, the male sex;
2. the diagnostic criteria that meets non-specific chronic prostatitis;
3. voluntary participation clinical testing, and signature Informed Consent Form.
The case exclusion standard:
1. merge the primary disease persons such as conscience kidney or hemopoietic system, the mental patient;
2. allergic constitution or to the known composition allergy sufferers of this product;
3. the anti-inflammatory drug treatment was used in medication in front 1 week;
4. carried out other clinical testing person in 1 week;
5. the researcher thinks and should not carry out clinical testing person;
6. do not meet diagnostic criteria person;
7. acute prostatitis patient, patients with prostate cancer.
The clinical testing method:
Adopt open to test from the clinic trial as contrast;
The patient injects deep rectum with the efficient monomer silver gel of example 5 preparations, and 1 of every day, every 3g is used in conjunction 15 days.
The clinical evaluation standard:
Recovery from illness: symptom disappears substantially behind the medication 15d, and integrated value reduces 〉=95%;
Produce effects: symptom is obviously improved behind the medication 15d, and integrated value reduces 〉=60%;
Effectively: doing well,improving behind the medication 15d, integrated value reduces 〉=30%;
Invalid: symptom is without obvious improvement behind the medication 15d, and integrated value reduces＜30%.
Clinical test results:
1, case performance
The case performance of table 4 embodiment of the invention 9 gathers
| The sick kind | Enter to organize number | Finish number | Number comes off |
| Chronic prostatitis | 72 | 69 | 3 |
2, result of the test
The result of the test of table 5 embodiment of the invention 9 gathers
Result of the test shows: total obvious effective rate of efficient monomer silver gel treatment chronic prostatitis provided by the invention is 44.92%, total effective rate is 89.95%, frequent micturition, odynuria, urine retention, soreness of waist and knee joint, the perineum part that can improve the chronic prostatitis initiation fall the symptoms such as swollen, and bad reaction does not occur in process of the test, prove that this product is safe and effective.
Embodiment 10
The efficient monomer silver washing lotion of research embodiment 6 preparation is to the result for the treatment of of acute and chronic rhinitis:
Case load:
Select acute rhinitis, rhinitis chronic patient each 72 examples, totally 144 examples.
The selection of case:
1. age l8～65 years old, male or female;
2. the diagnostic criteria that meets acute and chronic rhinitis;
3. voluntary participation clinical testing, and signature Informed Consent Form.
The case exclusion standard:
1. merge the primary disease persons such as conscience kidney or hemopoietic system, the mental patient;
2. pregnancy or women breast-feeding their children;
3. allergic constitution or to the known composition allergy sufferers of this product;
4. medication was used the anti-inflammatory drug curer in front 1 week;
5. carried out other clinical testing person in 1 week;
6. the researcher thinks and should not carry out clinical testing person;
7. do not meet diagnostic criteria person;
8. nasosinusitis patient.
The clinical testing method:
Adopt open to test from the clinic trial as contrast;
Using method: the efficient monomer silver washing lotion product of use-case 6 preparations, each 4 sprays, the about 0.2mL of every spray; Acute rhinitis patient every day 3 times, be used in conjunction 7 days; Rhinitis chronic patient every day 4 times, be used in conjunction 7 days.
The clinical evaluation standard:
Clinical cure: symptom and sign disappear substantially behind the medication 7d, and integrated value reduces 〉=95%;
Produce effects: cardinal symptom and sign are obviously improved behind the medication 7d, and integrated value reduces 〉=70%;
Effectively: cardinal symptom and sign are improved behind the medication 7d, and integrated value reduces 〉=30%;
Invalid: cardinal symptom and sign are without obvious improvement behind the medication 7d, and integrated value reduces＜30%.
Clinical test results:
1, case performance
The case performance of table 6 embodiment of the invention 10 gathers
2, result of the test
The result of the test of table 7 embodiment of the invention 10 gathers
Result of the test shows: total obvious effective rate of efficient monomer silver washing lotion treatment acute rhinitis provided by the invention is 56.34%, total effective rate is 94.37%, total obvious effective rate for the treatment of rhinitis chronic is 51.47%, total effective rate is 91.18%, can improve that its nasal obstruction that causes, rhinalgia, nasal cavity dryness are itched, nasal congestion, the symptom such as have a running nose, sneeze, bad reaction does not occur in process of the test, proves that this product is safe and effective.
Embodiment 11
The efficient monomer silver washing lotion of research embodiment 6 preparation is to various colpitic results for the treatment of:
Case load:
The patient of selecting bacteria vaginosis, VVC each 72 examples, totally 144 examples.
The selection of case:
1. age l8～65 years old, the women;
2. meet bacterial vaginosis BV, VVC, i.e. the diagnostic criteria of vulvovaginal candidiasis;
3. voluntary participation clinical testing, and signature Informed Consent Form.
The case exclusion standard:
1. age＜18 year old or age＞65 year old;
2. merge the primary disease persons such as conscience kidney or hemopoietic system, the mental patient;
3. pregnancy or women breast-feeding their children;
4. allergic constitution or to the known composition allergy sufferers of this product;
5. the anti-inflammatory drug treatment was used in medication in front 1 week;
6. carried out other clinical testing person in 1 week;
7. the researcher thinks and should not carry out clinical testing person;
8. do not meet diagnostic criteria person;
9. the women (virgin) who has sexual intercourse is not arranged.
The clinical testing method:
Adopt open to test from the clinic trial as contrast;
Patients with Bacterial Vaginosis: after cleaning vulva, the patient injects the vagina deep with the efficient monomer silver washing lotion product of example 6 preparations, and each 1 time sooner or later, each 30mL is used in conjunction 7 days;
Vulvovaginal candidiasis: using method is each 1 time sooner or later, with the efficient monomer silver washing lotion product of example 6 preparation with the direct wiping vulva of the mode of dipping in gauze or get the about 30mL ~ 40mL of product and pour in the basin, the volume ratio of pressing 1:10 adds warm water, carries out vulva and cleans, and uses continuously 7 days.
The clinical evaluation standard:
Recovery from illness: symptom and sign disappear substantially behind the medication 7d, and integrated value reduces 〉=90%;
Produce effects: cardinal symptom, sign are obviously improved behind the medication 7d, and integrated value reduces 〉=70%;
Effectively: cardinal symptom, sign are improved behind the medication 7d, and integrated value reduces 〉=30%;
Invalid: cardinal symptom and sign are without obvious improvement behind the medication 7d, and integrated value reduces＜30%.
Clinical test results:
1, case performance
The case performance of table 8 embodiment of the invention 11 gathers
2, result of the test
The result of the test of table 9 embodiment of the invention 11 gathers
Result of the test shows: total obvious effective rate of efficient monomer silver washing lotion treatment bacterial vaginosis BV provided by the invention is 60.87%, total effective rate is 89.86%, total obvious effective rate for the treatment of VVC is 57.97%, total effective rate is 91.30%, can improve the symptom such as itch, abnormal leucorrhea, private parts peculiar smell of its initiation, and bad reaction does not occur in process of the test, prove that this product is safe and effective.
Embodiment 12
The efficient monomer silver gel of research embodiment 7 preparation is to the result for the treatment of of chronic prostatitis:
Case load:
Select patients with chronic prostatitis totally 72 examples.
The selection of case:
1. age l8～65 years old, the male sex;
2. the diagnostic criteria that meets non-specific chronic prostatitis;
3. voluntary participation clinical testing, and signature Informed Consent Form.
The case exclusion standard:
1. merge the primary disease persons such as conscience kidney or hemopoietic system, the mental patient;
2. allergic constitution or to the known composition allergy sufferers of this product;
3. the anti-inflammatory drug treatment was used in medication in front 1 week;
4. carried out other clinical testing person in 1 week;
5. the researcher thinks and should not carry out clinical testing person;
6. do not meet diagnostic criteria person;
7. acute prostatitis patient, patients with prostate cancer.
The clinical testing method:
Adopt open to test from the clinic trial as contrast;
The patient injects deep rectum with the efficient monomer silver gel product of embodiment 7 preparations, and 1 of every day, every 3g is used in conjunction 15 days.
The clinical evaluation standard:
Recovery from illness: symptom disappears substantially behind the medication 15d, and integrated value reduces 〉=95%;
Produce effects: symptom is obviously improved behind the medication 15d, and integrated value reduces 〉=60%;
Effectively: doing well,improving behind the medication 15d, integrated value reduces 〉=30%;
Invalid: symptom is without obvious improvement behind the medication 15d, and integrated value reduces＜30%.
Clinical test results:
The case performance
The case performance of table 10 embodiment of the invention 12 gathers
| The sick kind | Enter to organize number | Finish number | Number comes off |
| Chronic prostatitis | 72 | 68 | 4 |
Result of the test
The result of the test of table 11 embodiment of the invention 12 gathers
Result of the test shows: total obvious effective rate of efficient monomer silver gel treatment chronic prostatitis provided by the invention is 45.59%, total effective rate is 88.24%, frequent micturition, odynuria, urine retention, soreness of waist and knee joint, the perineum part that can improve the chronic prostatitis initiation fall the symptoms such as swollen, and bad reaction does not occur in process of the test, prove that this product is safe and effective.
By above-described embodiment and comparative example as can be known, the present invention reacts under lower temperature, can prepare in the short period of time efficient monomer silver solution, and the efficient monomer silver granuel footpath homogeneous of preparation, be evenly distributed, and have good stability, can effectively treat all kinds of vaginitis, prostatitis and acute and chronic rhinitis with efficient monomer silver gel and the efficient monomer silver washing lotion of its preparation.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. the preparation method of an efficient monomer silver solution is characterized in that, comprising:
With the aqueous solution of silver-colored source compound with contain protectant aqueous solution, with the aqueous solution of reducing agent, react under the condition of stirring again, obtain efficient monomer silver solution;
Wherein, the speed of described stirring is 50r/min ~ 150r/min, and the temperature of described reaction is-5 ℃ ~ 10 ℃, and the time of described reaction is 30min ~ 200min.
2. method according to claim 1 is characterized in that, the mass ratio of described silver-colored source compound, protective agent and reducing agent is 1:(1 ~ 10): (0.05 ~ 0.5).
3. method according to claim 1 is characterized in that, the speed of described stirring is 90r/min ~ 110r/min.
4. method according to claim 1 is characterized in that, the temperature of described reaction is 0 ℃ ~ 5 ℃, and the time of described reaction is 150min ~ 180min.
5. method according to claim 1 is characterized in that, in the aqueous solution of described silver-colored source compound, the concentration of silver ion is 3.5g/L ~ 7.0g/L.
6. method according to claim 1 is characterized in that, described silver-colored source compound is selected from silver nitrate or silver ammonia complex.
7. method according to claim 1 is characterized in that, described protective agent is selected from any one or a few in polyvinyl alcohol, polyvinylpyrrolidone, gelatin, monohydric alcohol, polyalcohol, sorbierite, aromatic alcohol wax and the polynary arene; Described reducing agent is selected from sodium borohydride, H
2O
2, in formaldehyde, hydrazine hydrate, trisodium citrate, ascorbic acid, citric acid, ethanol, sugar, organic amine, polyalcohol and the ferrous salt any one or a few.
8. efficient monomer silver solution according to the preparation of the described method of claim 1-7 any one.
9. an efficient monomer silver gel is mixed by efficient monomer silver solution and assistant agent, and described efficient monomer silver solution is efficient monomer silver solution claimed in claim 8, and in the described efficient monomer silver gel, silver content is 200ppm ~ 500ppm.
10. an efficient monomer silver washing lotion is mixed by efficient monomer silver solution and water, and described efficient monomer silver solution is efficient monomer silver solution claimed in claim 8, and in the described efficient monomer silver washing lotion, silver content is 50ppm ~ 300ppm.
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