CN101773520A - Compound antimicrobial containing polyvalent silver ions and preparation method thereof - Google Patents

Compound antimicrobial containing polyvalent silver ions and preparation method thereof Download PDF

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CN101773520A
CN101773520A CN 201010120809 CN201010120809A CN101773520A CN 101773520 A CN101773520 A CN 101773520A CN 201010120809 CN201010120809 CN 201010120809 CN 201010120809 A CN201010120809 A CN 201010120809A CN 101773520 A CN101773520 A CN 101773520A
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silver
water
chitosan
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silver ion
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CN101773520B (en
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沈作兵
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Shenzhen Haldex Stc Biological Engineering Co ltd
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Abstract

The invention discloses a compound antimicrobial containing polyvalent silver ions, comprising a compound antibacterial gel preparation, a compound antibacterial water preparation and a compound antibacterial emulsifying preparation which are formed by respectively compounding an antibacterial reagent, a gel reagent, a water reagent and an emulsifying reagent. The antibacterial reagent contains a monovalent silver ion compound, a water soluble chitosan, EDTA, 1-methylbenzotriazole, propylene glycol and one or two of bivalent silver ion compound and trivalent silver ion compound. The invention has strong and lasting bacterial killing capability, can perform quick bacteria killing and deep bacteria killing, has strong anti-inflammatory function and the function on promoting the regeneration of epithelia, and can not generate acute or chronic accumulated toxic or side effect.

Description

Compound antimicrobial containing polyvalent silver ions and preparation method thereof
Technical field
The present invention relates to a kind of antiseptic prescription and preparation thereof, especially relate to a kind of antibacterial that mainly contains compound multivalence attitude silver ion, water-soluble chitosan, EDTA and preparation method thereof.
Background technology
As seen in relevant with the silver on the market at present antimicrobial product, classify from the form that exists of its silver: mainly contain two classes, a class is the nanometer silver product, and another kind of is unit price silver ion product.Nanometer silver can produce chronic accumulating because of powerful penetration capacity in human body, simple its sterilizing ability of unit price silver ion product is limited, can not deep layer sterilization, quick-acting sterilization, and above-mentioned two class silver products all to have its antiinflammatory action faint, do not have the cell regeneration of the human epidermal of promotion, do not have the effect that the self-defense function is organized in enhancing.
Therefore, above-mentioned nanometer silver antimicrobial product and unit price silver-ion antibiotic product are used for gynaecopathias such as female vagina and cervical erosion, during the treatment of infectious skin disease, it is higher to have relapse rate, especially suffer from intractable vaginitis patient weak curative effect, chronic accumulating, sterilizing power are not lasting, and no deep layer sterilization and epithelial repair wait scarce limit slowly.
Still it is strong and lasting to lack a kind of sterilizing power at present, sterilization rapidly, and the deep layer sterilization has strong antiinflammatory action, has the epithelial cell regeneration of promotion and can not produce the acute and chronic non-antibiotic safe environment protection type antimicrobial product of accumulating.
Summary of the invention
At problem set forth above, the object of the invention is to provide a kind of sterilizing power strong and lasting, sterilization rapidly, the deep layer sterilization, has strong antiinflammatory action, have the epithelial cell of promotion regeneration, can not produce the non-antibiotic safe environment protection type compound antimicrobial containing polyvalent silver ions of the acute and chronic toxic and side effects of accumulating.
The present invention realizes by following technical measures, a kind of complex antimicrobials that contains multivalence attitude silver ion comprises the three kinds of dosage forms of composite antibiosis gel, composite antibiosis water preparation, composite antibiosis Emulsion that are combined into gel reagents, water reagent, emulsification reagent respectively by antibacterial agent; This antibacterial agent contains unit price attitude silver iron compound, water-soluble chitosan, EDTA, 1-methyl benzotriazazole, propylene glycol, also contains any or two kinds in two unit price attitude silver iron compounds, the three valence state silver iron compounds.
The antibacterial agent optimization formula is: EDTA, silver nitrate, silver peroxide, propylene glycol, water-soluble chitosan, 1-methyl benzotriazazole, citric acid and carmine; The percentage by weight of each component is preferred: EDTA, 0.41%~1.49%; Silver nitrate, 0.16%~1.49%; Silver peroxide, 0.07%~0.08%; Propylene glycol, 74.57%~82.71%; Water-soluble chitosan, 0.08%~7.45%; The 1-methyl benzotriazazole, 7ppm~8ppm; Citric acid, 14.91%~16.54%; Carmine, 8ppm~75ppm.
The combination of any one or a few in the preferred oligo-chitosan of water-soluble chitosan, chitosan lactate, the chitosan quaternary amine.Wherein the preparation method of oligopolymerization chitosan sugar aqueous solution is: elder generation is dissolved in load weighted citric acid and then adds chitosan in the deionized water; Press H then 2O 2: H 2O=1: 10 add H 2O 2Insert microwave oven 5min heat time heating time of power 500w at last, promptly make the oligopolymerization chitosan sugar aqueous solution.
The weight ratio that contains the composite antibiosis gel each component of multivalence attitude silver ion is preferably antibacterial agent: carbomer: glycerol: deionized water=1: 0.07~0.08: 1.86~2.03: 4.52~5.04.Preparation method is: successively silver nitrate, 1-methyl benzotriazazole, silver peroxide, citric acid are added in the deionized water earlier, lucifuge left standstill 30 minutes; Then add EDTA, oligo-chitosan, propylene glycol, carmine more successively, mixing stirs gently, until forming pink aqueous solution; Add carbomer gradually, lucifuge left standstill 2 hours, treated its abundant swelling; Add glycerol and an amount of triethanolamine mixing at last, pH value reaches 5-7, stirs with the overhead type agitator, and speed is 450-500rpm; Until forming the gel that viscosity reaches the 30000-50000 centipoise, vacuum≤-condition of 0.095Mpa under vacuumizing and defoaming, can be packaged into composite antibiosis gel finished product.
The weight ratio that contains the composite antibiosis water preparation each component of multivalence attitude silver ion is preferably antibacterial agent: deionized water=1: 6.56~7.27.Preparation method is: successively silver nitrate, 1-methyl benzotriazazole, silver peroxide are added in the deionized water earlier, lucifuge left standstill 30 minutes; Then add EDTA, propylene glycol, carmine more successively, mixing stirs gently; Until forming peach aqueous solution, can be packaged into composite antibiosis water preparation finished product.
The weight ratio that contains the composite antibiosis Emulsion each component of multivalence attitude silver ion is preferably antibacterial agent: tween 20: Herba Menthae: Borneolum Syntheticum: deionized water=1: 1.12~1.22: 0.0014~0.0016: 0.0014~0.0016: 2.54~2.69.Preparation method is: successively silver nitrate, chitosan lactate, 1-methyl benzotriazazole, citric acid, silver peroxide are added in the deionized water earlier; Then add EDTA, propylene glycol, Herba Menthae, Borneolum Syntheticum, carmine, tween 20 successively; Stir gently until forming pink Emulsion, can be packaged into composite antibiosis Emulsion finished product.
The present invention is the complex antimicrobials that multiple Organic substances such as compound multivalence attitude silver ion, water-soluble chitosan, EDTA, propylene glycol, 1-methyl benzo three (nitrogen) azoles combine.Have wherein that unit price attitude silver ion has that sterilizing power is strong, the good characteristic of wide spectrum, lasting, no Drug resistance; The compound multivalence attitude silver ion that contains high valence state and unit price attitude silver ion also has, more rapidly sterilizing power more powerful than the silver-series antibacterial agent that only contains common unit price attitude silver ion when keeping common unit price attitude silver ion good characteristic, on the other hand, and Ag +, Ag 2+, Ag 3+It is ion, easily diffusion in gel, simultaneously because the physiologic barrier of vagina and skin is difficult for penetrating human vagina's wall epithelium again and epiderm skin enters the human lymphoid, blood circulation produces and accumulates, chitosan under little sour condition has electropositive, adsorbable electronegative antibacterial, make the negative charge skewness on bacteria cell wall and the cell membrane, the normal of interference cell wall synthesizes, broken the synthetic and dissolution equilibrium of the cell wall under the naturalness, make cell wall be tending towards dissolving, thing oozes out in the cell, and bacterolysis, death take place; Chitosan not only can suppress the generation of antibacterial, can also destroy existing antibacterial, reaches antibiotic, bacteriostatic effect, and the bactericidal action of water-soluble chitosan and compound multivalence attitude silver ion has constituted the antibiotic substance basis of antibacterial of the present invention.Therefore the present invention has potent, quick-acting, wide spectrum, lasting sterilization, the characteristics of no body accumulation.
Water-soluble chitosan has certain slow release, control-release function.Compound multivalence attitude silver ion can slowly be discharged.The trip amino that chitosan and derivative molecular thereof carry, has certain positive charge, when chitosan and derivant thereof and cell membrane are done the time spent, cellularity changes on the tight film that acts on of feasible and albumen, cause transmembrane channel open, the permeability of film is improved, and makes multivalence attitude silver ion be penetrated into the vaginal wall fold place by contact, and its built-in pathogenic bacteria is killed.Simultaneously can absorb inflammatory exudate and reach antipruritic, antiinflammatory purpose.Moreover; Chitosan also helps to regulate the cell growth, and N-second phthalein amino-D-glycosamine is the essential nutrient substance of epidermal growth, can promote epithelial growth, waits biological activity.The self-contained positive charge of chitosan helps hematoblastic gathering, and can activate blood coagulation system, makes erythrocyte form clot.Simultaneously; Test and clinical effectiveness show that silver ion can be strengthened the epithelization process of wound when reducing infection, and play the effect of antiinflammatory by the effect of metalloproteases.Like this chitosan and compound multivalence silver both constituted antiinflammatory of the present invention jointly, promoted the main matter basis of epithelial repair.Therefore the present invention also has the deep layer sterilization, hemostasis, antipruritic, antiinflammatory, alleviates wound pain, promotes the impaired epithelium of inflammation more multiple, strengthens the characteristics of vagina defense function.
The carbomer strong adhesion, the holdup time is long, and propylene glycol is the epidermis penetration enhancer, can impel multivalence attitude silver ion to be penetrated into the vaginal wall fold place by contact jointly with water-soluble chitosan, and its built-in pathogenic bacteria is killed.Further improve the deep layer sterilization effects.EDTA can absorb ultraviolet, effectively prevents the viscosity degradation that carbomer gel causes because of ultraviolet radiation, and EDTA, 1-methyl benzo three (nitrogen) azoles can prevent the discoloration problem that multivalence attitude silver ion causes effectively jointly, improve its product stability.Therefore the present invention also has deep layer sterilization, slow release sterilization, antiinflammatory, the characteristics of stable performance.
Therefore the antibacterial of the present invention broad-spectrum antibacterial property that is had that both had active silver-series antibacterial agent, potent property, lasting effect, no Drug resistance, has the water-soluble chitosan antiinflammatory again, the characteristic of short impaired epitheliosis reparation, make the physiological barrier of the vagina of human body self and skin obtain the advantage of rebuilding fast, can effectively reduce infective vaginitis, cervicitis and dermopathic relapse rate.Be a kind of treat infective vaginitis and dermopathic wide spectrum, potent, long-acting, relapse rate is low, the antibacterial of stable performance.
The specific embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1:
Carbomer 980 1g
Glycerol 15g
EDTA 0.05g
Silver nitrate 0.2g
Silver peroxide 0.01g
Propylene glycol 10g
Oligo-chitosan 1g
1-methyl benzotriazazole 0.0001g
Citric acid 2g
Carmine 0.01g
Deionized water 70.7299g
Method for making:
Successively silver nitrate, 1-methyl benzotriazazole, silver peroxide, citric acid are added in the deionized water earlier, lucifuge left standstill 30 minutes; Then add EDTA, oligo-chitosan, propylene glycol, carmine more successively, mixing stirs gently, until forming pink aqueous solution; Add carbomer 980 gradually, lucifuge left standstill 2 hours, treated its abundant swelling; Add glycerol and triethanolamine mixing at last, regulate pH value and reach 5-7, stir with the overhead type agitator, speed is 450-500rpm; Until forming gel, (viscosity reaches the 30000-50000 centipoise) vacuumizing and defoaming (vacuum for≤-0.095Mpa), be packaged into composite antibiosis gel finished product.
Embodiment 2:
EDTA 0.05g
Silver nitrate 0.05g
Silver peroxide 0.01g
Propylene glycol 10g
Oligo-chitosan 1g
1-methyl benzotriazazole 0.0001g
Citric acid 2g
Carmine 0.01g
Deionized water 86.9799g
Method for making:
Successively silver nitrate, 1-methyl benzotriazazole, silver peroxide, citric acid are added in the deionized water earlier, lucifuge left standstill 30 minutes; Then add EDTA, propylene glycol, carmine more successively, mixing stirs gently, until forming peach aqueous solution, is packaged into composite antibiosis water preparation finished product.
Embodiment 3:
Carbomer 980 1g
Glycerol 15g
EDTA 0.05g
Silver nitrate 0.2g
Silver peroxide 0.01g
Propylene glycol 10g
Chitosan lactate 0.5g
1-methyl benzotriazazole 0.0001g
Citric acid 2g
Carmine 0.01g
Herba Menthae 0.02g
Borneolum Syntheticum 0.02g
Deionized water 71.1899g
Method for making:
Successively silver nitrate, chitosan lactate, 1-methyl benzotriazazole, citric acid, silver peroxide are added in the deionized water earlier, lucifuge left standstill 30 minutes, then add EDTA, propylene glycol, Herba Menthae, Borneolum Syntheticum, carmine more successively, form peach aqueous solution; Add carbomer 980 gradually, lucifuge left standstill 2 hours, treated its abundant swelling; Add glycerol and an amount of triethanolamine mixing at last, pH value reaches 5-7, stirs with the overhead type agitator, and speed is 450-500rpm; Until forming gel, (viscosity reaches the 30000-50000 centipoise) vacuumizing and defoaming (vacuum for≤-0.095Mpa), be packaged into composite antibiosis gel finished product.
Embodiment 4:
Sodium carboxymethyl cellulose 6g
Glycerol 15g
Ethyl hydroxybenzoate 0.02g
EDTA 0.05g
Silver nitrate 0.2g
Silver peroxide 0.01g
Propylene glycol 10g
Chitosan quaternary amine 0.5g
1-methylbenzotrazole 0.0001g
Citric acid 2g
Carmine 0.01g
Herba Menthae 0.02g
Borneolum Syntheticum 0.02g
Deionized water 66.1699g
Method for making: get ethyl hydroxybenzoate earlier and be dissolved in the hot deionized water, then add sodium carboxymethyl cellulose and glycerol, add silver nitrate, chitosan lactate, 1-methylbenzotrazole, citric acid, silver peroxide then successively; Lucifuge left standstill 30 minutes, then added EDTA, propylene glycol, Herba Menthae, Borneolum Syntheticum, carmine successively again, formed peach aqueous solution; At last, use the overhead type agitator at normal temperatures, speed is 450-500rpm, stirs into gel (viscosity reaches the 30000-50000 centipoise); Vacuumizing and defoaming (vacuum is≤-0.095Mpa), be packaged into composite antibiosis gel finished product.
Embodiment 5:
EDTA 0.05g
Silver nitrate 0.2g
Silver peroxide 0.01g
Propylene glycol 10g
Chitosan lactate 0.5g
1-methylbenzotrazole 0.0001g
Citric acid 2g
Carmine 0.01g
Tween 20 15g
Herba Menthae 0.02g
Borneolum Syntheticum 0.02g
Deionized water 72.1899g
Method for making:
Successively silver nitrate, chitosan lactate, 1-methylbenzotrazole, citric acid, silver peroxide are added in the deionized water earlier, lucifuge left standstill 30 minutes, then add EDTA, propylene glycol, Herba Menthae, Borneolum Syntheticum, carmine more successively, tween 20, stir gently until forming peach Emulsion, be packaged into composite antibiosis Emulsion finished product.
Embodiment 6:
Carbomer 980 1g
Glycerol 15g
EDTA 0.05g
Silver nitrate 0.2g
Silver peroxide 0.01g
Propylene glycol 10g
Chitosan quaternary amine 0.5g
1-methylbenzotrazole 0.0001g
Citric acid 2g
Carmine 0.01g
Herba Menthae 0.02g
Borneolum Syntheticum 0.02g
Deionized water 71.1899g
Method for making:
Successively silver nitrate, chitosan quaternary amine, 1-methylbenzotrazole, citric acid, silver peroxide are added in the deionized water earlier, lucifuge left standstill 30 minutes, then added EDTA, propylene glycol, Herba Menthae, Borneolum Syntheticum, carmine more successively, formed peach aqueous solution.Add carbomer 980 gradually, lucifuge left standstill 2 hours, treated its abundant swelling.Add glycerol and an amount of triethanolamine mixing at last, pH value reaches 5-7, stirs with the overhead type agitator, and speed is 450-500rpm; Until forming gel, (viscosity reaches the 30000-50000 centipoise) vacuumizing and defoaming (vacuum for≤-0.095Mpa), be packaged into composite antibiosis gel finished product.
Antibacterial, the bactericidal assay of the compound multivalence attitude of the present invention silver ion chitosan compound anti-bacteria agent:
Figure GSA00000027783200111
The biological safety test of the compound multivalence attitude of the present invention silver ion chitosan compound anti-bacteria agent:
1, cell toxicity test, the reaction classification is not more than 2.
2, hypersensitive test, the reaction classification is not more than 1.
3, mucosa irritation test, reaction is kept the score and is not more than 1.
More than be the present invention to be contained the multiple dosage form of complex antimicrobials of multivalence attitude silver ion and prescription and manufacture method set forth; be used for helping to understand the present invention; but embodiments of the present invention are not restricted to the described embodiments; any change that does not deviate under the principle of the invention to be done, modification, substitute, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (9)

1. complex antimicrobials that contains multivalence attitude silver ion is characterized in that: comprise the three kinds of dosage forms of composite antibiosis gel, composite antibiosis water preparation, composite antibiosis Emulsion that are combined into gel reagents, water reagent, emulsification reagent respectively by antibacterial agent; This antibacterial agent contains unit price attitude silver iron compound, water-soluble chitosan, EDTA, 1-methyl benzotriazazole, propylene glycol, also contains any or two kinds in two unit price attitude silver iron compounds, the three valence state silver iron compounds.
2. the complex antimicrobials that contains multivalence attitude silver ion according to claim 1 is characterized in that: the composition of described antibacterial agent is EDTA, silver nitrate, silver peroxide, propylene glycol, water-soluble chitosan, 1-methyl benzotriazazole, citric acid and carmine; The percentage by weight of each component is: EDTA, 0.41%~1.49%; Silver nitrate, 0.16%~1.49%; Silver peroxide, 0.07%~0.08%; Propylene glycol, 74.57%~82.71%; Water-soluble chitosan, 0.08%~7.45%; The 1-methyl benzotriazazole, 7ppm~8ppm; Citric acid, 14.91%~16.54%; Carmine, 8ppm~75ppm.
3. the complex antimicrobials that contains multivalence attitude silver ion according to claim 1 and 2 is characterized in that: described water-soluble chitosan is any one or a few the combination in oligo-chitosan, chitosan lactate, the chitosan quaternary amine.
4. the complex antimicrobials that contains multivalence attitude silver ion according to claim 1 and 2, the weight ratio that it is characterized in that composite antibiosis gel each component is antibacterial agent: carbomer: glycerol: deionized water=1: 0.07~0.08: 1.86~2.03: 4.52~5.04.
5. the complex antimicrobials that contains multivalence attitude silver ion according to claim 4, the preparation method that it is characterized in that the composite antibiosis gel is: successively silver nitrate, 1-methyl benzotriazazole, silver peroxide, citric acid are added in the deionized water earlier, lucifuge left standstill 30 minutes; Then add EDTA, oligo-chitosan, propylene glycol, carmine more successively, mixing stirs gently, until forming pink aqueous solution; Add carbomer gradually, lucifuge left standstill 2 hours, treated its abundant swelling; Add glycerol and an amount of triethanolamine mixing at last, pH value reaches 5-7, stirs with the overhead type agitator, and speed is 450-500rpm; Until forming the gel that viscosity reaches the 30000-50000 centipoise, vacuum≤-condition of 0.095Mpa under vacuumizing and defoaming, can be packaged into composite antibiosis gel finished product.
6. the complex antimicrobials that contains multivalence attitude silver ion according to claim 1 and 2 is characterized in that the weight ratio of composite antibiosis water preparation each component is antibacterial agent: deionized water=1: 6.56~7.27.
7. the complex antimicrobials that contains multivalence attitude silver ion according to claim 6 is characterized in that the preparation method of composite antibiosis water preparation is: successively silver nitrate, 1-methyl benzotriazazole, silver peroxide are added in the deionized water earlier, lucifuge left standstill 30 minutes; Then add EDTA, propylene glycol, carmine more successively, mixing stirs gently; Until forming peach aqueous solution, can be packaged into composite antibiosis water preparation finished product.
8. the complex antimicrobials that contains multivalence attitude silver ion according to claim 1 and 2, the weight ratio that it is characterized in that composite antibiosis Emulsion each component is antibacterial agent: tween 20: Herba Menthae: Borneolum Syntheticum: deionized water=1: 1.12~1.22: 0.0014~0.0016: 0.0014~0.0016: 2.54~2.69.
9. the complex antimicrobials that contains multivalence attitude silver ion according to claim 8 is characterized in that the preparation method of composite antibiosis Emulsion is: successively silver nitrate, chitosan lactate, 1-methyl benzotriazazole, citric acid, silver peroxide are added in the deionized water earlier; Then add EDTA, propylene glycol, Herba Menthae, Borneolum Syntheticum, carmine, tween 20 successively; Stir gently until forming pink Emulsion, can be packaged into composite antibiosis Emulsion finished product.
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CN102416041A (en) * 2011-12-13 2012-04-18 成都默森医药开发有限公司 Antibacterial and anti-inflammatory Chinese medicinal composition and preparation method thereof
CN102475676A (en) * 2010-11-29 2012-05-30 西安三八妇乐健康产业有限公司 Silver ion gynaecological gel
CN102824363A (en) * 2012-09-21 2012-12-19 张晋瑞 Antibacterial agent
CN103385926A (en) * 2013-07-09 2013-11-13 武汉烺祺生物科技有限公司 Antibiosis gel for curing cervical and vaginal diseases of gynaecology
CN104706668A (en) * 2015-04-02 2015-06-17 苏州泰利三佳纳米科技有限公司 Female care solution containing silver ions and preparation method of female care solution
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CN106857660A (en) * 2017-04-14 2017-06-20 苏州泰利三佳纳米科技有限公司 A kind of disinfecting mite-removing agent of silver ion and preparation method thereof
CN107261796A (en) * 2017-06-20 2017-10-20 广州市科瑨材料科技有限公司 Antibacterial is except aldehyde cleanser and preparation method thereof
CN107913394A (en) * 2017-11-22 2018-04-17 苏州祖原堂纳米科技有限公司 A kind of koro gel containing nano-silver ionic
CN109646456A (en) * 2018-12-31 2019-04-19 四川金凯医疗器械有限公司 It is a kind of for treating the new type gel of periodontitis
CN112494514A (en) * 2020-09-18 2021-03-16 广州卡士德汽车用品有限公司 Bactericidal disinfectant and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN102475676A (en) * 2010-11-29 2012-05-30 西安三八妇乐健康产业有限公司 Silver ion gynaecological gel
CN102416041A (en) * 2011-12-13 2012-04-18 成都默森医药开发有限公司 Antibacterial and anti-inflammatory Chinese medicinal composition and preparation method thereof
CN102824363A (en) * 2012-09-21 2012-12-19 张晋瑞 Antibacterial agent
TWI491354B (en) * 2012-12-26 2015-07-11 Ind Tech Res Inst Antimicrobial material and method for fabricating the same
CN103385926A (en) * 2013-07-09 2013-11-13 武汉烺祺生物科技有限公司 Antibiosis gel for curing cervical and vaginal diseases of gynaecology
CN104706668A (en) * 2015-04-02 2015-06-17 苏州泰利三佳纳米科技有限公司 Female care solution containing silver ions and preparation method of female care solution
CN106857660A (en) * 2017-04-14 2017-06-20 苏州泰利三佳纳米科技有限公司 A kind of disinfecting mite-removing agent of silver ion and preparation method thereof
CN107261796A (en) * 2017-06-20 2017-10-20 广州市科瑨材料科技有限公司 Antibacterial is except aldehyde cleanser and preparation method thereof
CN107913394A (en) * 2017-11-22 2018-04-17 苏州祖原堂纳米科技有限公司 A kind of koro gel containing nano-silver ionic
CN109646456A (en) * 2018-12-31 2019-04-19 四川金凯医疗器械有限公司 It is a kind of for treating the new type gel of periodontitis
CN112494514A (en) * 2020-09-18 2021-03-16 广州卡士德汽车用品有限公司 Bactericidal disinfectant and preparation method thereof

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