CN108385374A - A kind of preparation method of silver-loaded silica antiseptic - Google Patents
A kind of preparation method of silver-loaded silica antiseptic Download PDFInfo
- Publication number
- CN108385374A CN108385374A CN201810146267.XA CN201810146267A CN108385374A CN 108385374 A CN108385374 A CN 108385374A CN 201810146267 A CN201810146267 A CN 201810146267A CN 108385374 A CN108385374 A CN 108385374A
- Authority
- CN
- China
- Prior art keywords
- silver
- loaded silica
- antiseptic
- loaded
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of preparation methods of silver-loaded silica antiseptic, first prepare the hydrophobic silica colloidal sol of methyl modification；Silver-loaded silica colloidal sol is being prepared by addition silver nitrate solution, reducing agent, dry, grinding obtains silver-loaded silica material after roasting；The silver-loaded silica material after roasting is dispersed in the distilled water containing TEA again, is added in the ethanol solution of silane-containing coupling agent KH -560 and carries out high-speed stirred, adjusts pH value to get the silver-loaded silica antibacterial dispersion liquid of high concentration；Silver-loaded silica antibacterial dispersion liquid is diluted, adhesive is added afterwards, silver-loaded silica antiseptic is made.A kind of preparation method of silver-loaded silica antiseptic of the present invention, silver is added into classical antibacterial agents, the nano silver of formation can improve antibacterial effect, and safety higher, long-term effect and heat resistance are also superior to classical antibacterial agents.
Description
Technical field
The invention belongs to biological antibiotic technical fields, and in particular to a kind of preparation method of silver-loaded silica antiseptic.
Background technology
Textile plays a very important role in people's lives, have hide body cold extermination, windproof, grease proofing, antifouling, radiation protection,
The functions such as Waterproof Breathable.And textile can be infected in use by the dirt from human body and environment, cause pathogenic bacteria
Breeding and transmission, to causing damages to the health of human body, common bacterium include staphylococcus aureus, Escherichia coli,
Pseudomonas aeruginosa, aflatoxins and Candida albicans etc..
Textile is mostly fibre, and fiber belongs to porous material, can also after especially many fibre superposition braidings
The layered body for forming countless gaps easily adsorbs bacterium, and lesion is easily formed after human contact, and textile itself, which will also result in, to decline
Solution, discoloration, generation peculiar smell etc..Therefore, antiseptic is added in textile, assigns antibacterial textile, antibacterial and sterilization function,
Have great importance, the use value of textile itself can not only be protected, not by degradations such as moulds；And prevent microorganism
Propagation through textile allows user from bacterial infestation, reduces the cross-infection rate of public environment, prevents bacterium on the fabric
It constantly breeds and generates foul smell.
Currently, having carried out a large amount of research in terms of antibacterial textile finishing functions both at home and abroad, make great progress,
Antimicrobial product has been expanded to fields such as gym suit, carpet, tent, umbrella, medical supplies, develop economical and efficient, have no toxic side effect,
The good textile antimicrobial agent of durability has become hot spot.Textile antimicrobial agent need to have broad-spectrum antibacterial property, persistence, weather-proof
The features such as property, safety and bacterium are not likely to produce drug resistance.Generally acknowledge antiseptic classification have natural antibacterial agent, organic antibacterial agent,
Inorganic antiseptic three classes.Organic antibacterial agent has antibacterial speed fast, easy to process, has the advantages that special efficacy to mould, but there is peace
It is complete that property is poor, is also easy to produce the shortcomings of microorganism drug resistance, chemical constitution are unstable, heat resistance is poor, easy to migrate in the plastic；It is inorganic
Antiseptic has the advantages that safe, durable heat-resist, but photocatalyst-type inorganic antiseptic must have suitable wave band
Ultraviolet light could play bactericidal effect, do not have antibacterial spectrum so as to cause photocatalyst-type anti-biotic agent.It is anti-to explore textile
Microbial inoculum low-carbon green synthetic method, exploitation has no toxic side effect to environment and human-body safety, high-efficiency antimicrobial is mould proof and to textile
The antibacterial agent of ultimate strength, hygroscopicity and gas permeability without negative effect is the development trend of textiles antibacterial finishing.
The grain size of nano material has great specific surface area generally between 1~100nm, while also having quantum effect
Should and small-size effect, and silver material have antibacterial functions, therefore nano silver become nano antibacterial agent research hotspot, by silver be
Antibacterial functions of the antiseptic for fabric are modified, and have enough safeties, long-term effect and heat resistance also superior to traditional antibacterial
Agent, and can effectively improve the anti-microbial property of nano silver antimicrobials by adjusting the additive amount of silver.
Invention content
The object of the present invention is to provide a kind of preparation methods of silver-loaded silica antiseptic, solve existing antiseptic
The problem of low, the durable heat resistance difference of safety, meanwhile, it is capable to which the additive amount by adjusting nano silver, it is anti-effectively to improve it
Bacterium performance.
The technical solution adopted in the present invention is a kind of preparation method of silver-loaded silica antiseptic, specifically according to
Lower step is implemented：
Step 1, the hydrophobic silica colloidal sol for preparing methyl modification
Ethyl orthosilicate (TEOS), dimethyldimethoxysil,ne (DMDMS), absolute ethyl alcohol (EtOH) are placed in ice-water bath
In, 30~60min of stirring makes it be sufficiently mixed for homogeneous phase solution, and distilled water and nitric acid is slowly added dropwise while stirring homogeneous phase solution
The mixture of solution, is stirred and 2~5h postcoolings that flow back are to room temperature, obtains the hydrophobic silica colloidal sol of methyl modification；
Step 2 prepares silver-loaded silica colloidal sol
Silver nitrate solution is added when the hydrophobic silica colloidal sol that the methyl obtained in whipping step 1 is modified, adds
It is complete to continue 30~60min of stirring；It is subsequently added into reducing agent, is stirred continuously in adding procedure, has added and has continued 30~60min of stirring
Postcooling obtains silver-loaded silica colloidal sol to room temperature；
Step 3 prepares silver-loaded silica material
By in step 2 to silver-loaded silica colloidal sol be placed in culture dish, be ground into after drying under vacuum conditions
Fine particles, and 2~5h is roasted under air or nitrogen atmosphere, obtain silver-loaded silica material；
Step 4, the silver-loaded silica antibacterial dispersion liquid for preparing high concentration
The silver-loaded silica material obtained in step 3 is distributed to dissolved with a certain amount of triethanolamine by step 4.1
(TEA) in distilled water, mixed liquor A is obtained, then that mixed liquor A is added to the ethyl alcohol containing a certain amount of silane coupling agent KH -560 is molten
In liquid, adding procedure is stirred continuously ethanol solution, obtains mixed liquid B；
Step 4.2, the pH value for adjusting mixed liquid B are 8~9, continue 3~4h of stirring, obtain the load silver titanium dioxide of high concentration
Silicon antibacterial dispersion liquid；
Step 5 prepares silver-loaded silica antiseptic
Under ul-trasonic irradiation, according to actual demand, the silver-loaded silica antibacterial of the high concentration obtained in dilution step 4
Dispersion liquid obtains silver-loaded silica antibacterial dilution, then a certain amount of bonding is added into silver-loaded silica antibacterial dilution
Agent obtains silver-loaded silica antiseptic.
The features of the present invention also characterized in that
Ethyl orthosilicate (TEOS) in step 1：Dimethyldimethoxysil,ne (DMDMS)：Absolute ethyl alcohol (EtOH)：Distillation
Water：The molar ratio of nitric acid is 1：0.3~0.6：6~10：6~9：0.04~0.10.
A concentration of 1.0mol/L~2.0mol/L of salpeter solution in step 1, reflux temperature are 50~75 DEG C.
Reducing agent in step 2 is N,N-dimethylformamide or urea liquid.
The molar ratio of silver nitrate and ethyl orthosilicate (TEOS) in step 1 is 0.05~0.25 in step 2：1, silver nitrate is molten
A concentration of 0.5mol/L~2.0mol/L of liquid.
Vacuum drying temperature is 20~60 DEG C in step 3, roasting be first be warming up to 300 with 0.5~5.0 DEG C/min~
450 DEG C, roast 2~5h after again with 0.5~3.0 DEG C/min cooling downs to room temperature.
The percent by volume of triethanolamine (TEA) is 2~3% in distilled water in step 4, silane coupling agent in ethanol solution
The percent by volume of KH -560 is 2~3%.
The percent by volume that adhesive is added in step in silver-loaded silica antibacterial dispersion liquid is 3~5%.
The percent by volume of N,N-dimethylformamide is 20~40% in the hydrophobic silica colloidal sol that methyl is modified.
Urea liquid is that urea presses 1 with absolute ethyl alcohol:1 volume ratio configures, urea liquid a concentration of 0.5~
The molar ratio of 1.5mol/L, urea and silver nitrate is 1:1.
The beneficial effects of the invention are as follows：
(1) preparation method of a kind of silver-loaded silica antiseptic of the invention, shape in classical antibacterial agents is added by silver
At nano silver, the antibacterial effect of antiseptic is greatly improved, meanwhile, the safety higher of antiseptic, long-term effect and heat resistance
Also superior to classical antibacterial agents；
(2) preparation method of a kind of silver-loaded silica antiseptic of the invention, the additive amount by adjusting silver can have
Improve the anti-microbial property of antiseptic in effect ground.
Description of the drawings
Fig. 1 is a kind of antiseptic of the different silver contents of doping prepared by the preparation method of silver-loaded silica antiseptic of the present invention
To the comparison diagram of Escherichia coli antibiotic rate.
Specific implementation mode
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
A kind of preparation method of silver-loaded silica antiseptic of the present invention, is specifically implemented according to the following steps：
Step 1, the hydrophobic silica colloidal sol for preparing methyl modification
Ethyl orthosilicate (TEOS), dimethyldimethoxysil,ne (DMDMS), absolute ethyl alcohol (EtOH) are placed in ice-water bath
In, 30~60min of stirring makes it be sufficiently mixed for homogeneous phase solution, and distilled water and concentration is slowly added dropwise while stirring homogeneous phase solution
For the mixture of the salpeter solution of 1.0mol/L~2.0mol/L, stirs and 2~5h postcoolings that flow back at 50~75 DEG C is to room temperature,
Obtain the hydrophobic silica colloidal sol of methyl modification, wherein ethyl orthosilicate (TEOS)：Dimethyldimethoxysil,ne
(DMDMS)：Absolute ethyl alcohol (EtOH)：Distilled water：The molar ratio of nitric acid is 1：0.3~0.6：6~10：6~9：
0.04~0.10；
Step 2 prepares silver-loaded silica colloidal sol
Be added when the hydrophobic silica colloidal sol that the methyl that is obtained in whipping step 1 is modified a concentration of 0.5mol/L~
The silver nitrate solution of 2.0mol/L has added and has continued 30~60min of stirring, wherein silver nitrate and ethyl orthosilicate in step 1
(TEOS) molar ratio is 0.05~0.25：1；
It is subsequently added into the n,N-Dimethylformamide of 20~40% (v/v), is stirred continuously in adding procedure, has added continuation
30~60min postcoolings are stirred to room temperature to get to silver-loaded silica colloidal sol；
Or urea is added and presses 1 with absolute ethyl alcohol:The urea for a concentration of 0.5~1.5mol/L that 1 volume ratio is configured to is molten
Liquid, wherein the molar ratio of urea and silver nitrate is 1:1, it is stirred continuously in adding procedure, has added and continued 30~60min of stirring
Postcooling is to room temperature to get to silver-loaded silica colloidal sol；
Step 3 prepares silver-loaded silica material
By in step 2 to silver-loaded silica colloidal sol be placed in culture dish, do under 20~60 DEG C of the vacuum environment
It is ground into fine particles after dry, and 300~450 DEG C is warming up to 0.5~5.0 DEG C/min under air or nitrogen atmosphere, roasting 2~
Silver-loaded silica material is obtained with 0.5~3.0 DEG C/min cooling downs to room temperature again after 5h；
Step 4, the silver-loaded silica antibacterial dispersion liquid for preparing high concentration
The silver-loaded silica material obtained in step 3 is distributed to three second dissolved with 2~3% (v/v) by step 4.1
In the distilled water of hydramine (TEA), mixed liquor A is obtained, then mixed liquor A is added to the silane coupling agent KH-containing 2~3% (v/v)
In 560 ethanol solution, adding procedure is stirred continuously ethanol solution, obtains mixed liquid B；
Step 4.2, the pH value for adjusting mixed liquid B are 8~9, continue 3~4h of stirring to get to the load silver dioxy of high concentration
SiClx antibacterial dispersion liquid.
Step 5 prepares silver-loaded silica antiseptic
Under ul-trasonic irradiation, according to actual demand, the silver-loaded silica antibacterial of the high concentration obtained in dilution step 4
Dispersion liquid obtains silver-loaded silica antibacterial dilution, then 3~5% (v/v) is added into silver-loaded silica antibacterial dilution
Adhesive, obtain silver-loaded silica antiseptic.
Embodiment 1
A kind of preparation method of silver-loaded silica antiseptic, is specifically implemented according to the following steps：
Step 1, the hydrophobic silica colloidal sol for preparing methyl modification
Ethyl orthosilicate (TEOS), dimethyldimethoxysil,ne (DMDMS), absolute ethyl alcohol (EtOH) are placed in ice-water bath
In, stirring 30min makes it be sufficiently mixed for homogeneous phase solution, be slowly added dropwise while stirring homogeneous phase solution distilled water with it is a concentration of
The mixture of the salpeter solution of 1.0mol/L, is stirred and the 2h postcoolings that flow back at 75 DEG C are to room temperature, obtains the hydrophobic of methyl modification
Property silicon dioxide gel, wherein ethyl orthosilicate (TEOS)：Dimethyldimethoxysil,ne (DMDMS)：Absolute ethyl alcohol
(EtOH)：Distilled water：The molar ratio of nitric acid is 1：0.3：6：9：0.04；
Step 2 prepares silver-loaded silica colloidal sol
It is added a concentration of 0.5mol/L's when the hydrophobic silica colloidal sol that the methyl obtained in whipping step 1 is modified
The molar ratio of silver nitrate solution, silver nitrate and ethyl orthosilicate (TEOS) in step 1 is 0.05：1, it has added and has continued to stir
30min；It is subsequently added into the n,N-Dimethylformamide of 20% (v/v), is stirred continuously in adding procedure, has been added and continued to stir
30min postcoolings obtain silver-loaded silica colloidal sol to room temperature；
Step 3 prepares silver-loaded silica material
By in step 2 to silver-loaded silica colloidal sol be placed in culture dish, after dry under 20 DEG C of the vacuum environment
It is ground into fine particles, and 300 DEG C is warming up to 0.5 DEG C/min under air or nitrogen atmosphere, roast after 2h again with 0.5 DEG C/min
Cooling down obtains silver-loaded silica material to room temperature；
Step 4, the silver-loaded silica antibacterial dispersion liquid for preparing high concentration
The silver-loaded silica material obtained in step 3 is distributed to the triethanolamine dissolved with 2% (v/v) by step 4.1
(TEA) in distilled water, mixed liquor A is obtained, then mixed liquor A is added to the second of the silane coupling agent KH -560 containing 2% (v/v)
In alcoholic solution, adding procedure is stirred continuously ethanol solution, obtains mixed liquid B；
Step 4.2, the pH value for adjusting mixed liquid B are 8, continue to stir 3h, obtain the silver-loaded silica antibacterial of high concentration
Dispersion liquid.
Step 5 prepares silver-loaded silica antiseptic
Under ul-trasonic irradiation, according to actual demand, the silver-loaded silica antibacterial of the high concentration obtained in dilution step 4
Dispersion liquid obtains silver-loaded silica antibacterial dilution, then is added 3% (v/v's) into silver-loaded silica antibacterial dilution
Adhesive obtains silver-loaded silica antiseptic.
Embodiment 2
A kind of preparation method of silver-loaded silica antiseptic, is specifically implemented according to the following steps：
Step 1, the hydrophobic silica colloidal sol for preparing methyl modification
Ethyl orthosilicate (TEOS), dimethyldimethoxysil,ne (DMDMS), absolute ethyl alcohol (EtOH) are placed in ice-water bath
In, stirring 40min makes it be sufficiently mixed for homogeneous phase solution, be slowly added dropwise while stirring homogeneous phase solution distilled water with it is a concentration of
The mixture of the salpeter solution of 1.5mol/L, is stirred and the 3h postcoolings that flow back at 65 DEG C are to room temperature, obtains the hydrophobic of methyl modification
Property silicon dioxide gel, wherein ethyl orthosilicate (TEOS)：Dimethyldimethoxysil,ne (DMDMS)：Absolute ethyl alcohol
(EtOH)：Distilled water：The molar ratio of nitric acid is 1：0.4：8：7：0.08；
Step 2 prepares silver-loaded silica colloidal sol
It is added a concentration of 1.0mol/L's when the hydrophobic silica colloidal sol that the methyl obtained in whipping step 1 is modified
The molar ratio of silver nitrate solution, silver nitrate and ethyl orthosilicate (TEOS) in step 1 is 0.10：1, it has added and has continued to stir
40min；It is subsequently added into the n,N-Dimethylformamide of 30% (v/v), is stirred continuously in adding procedure, has been added and continued to stir
40min postcoolings obtain silver-loaded silica colloidal sol to room temperature；
Step 3 prepares silver-loaded silica material
By in step 2 to silver-loaded silica colloidal sol be placed in culture dish, after dry under 40 DEG C of the vacuum environment
It is ground into fine particles, and 350 DEG C is warming up to 1.5 DEG C/min under air or nitrogen atmosphere, roast after 3h again with 2.0 DEG C/min
Cooling down obtains silver-loaded silica material to room temperature；
Step 4, the silver-loaded silica antibacterial dispersion liquid for preparing high concentration
The silver-loaded silica material obtained in step 3 is distributed to three ethyl alcohol dissolved with 2.5% (v/v) by step 4.1
In the distilled water of amine (TEA), mixed liquor A is obtained, then mixed liquor A is added to the silane coupling agent KH -560 containing 2.5% (v/v)
Ethanol solution in, adding procedure is stirred continuously ethanol solution, obtains mixed liquid B；
Step 4.2, the pH value for adjusting mixed liquid B are 8, continue to stir 3.5h, and the silver-loaded silica for obtaining high concentration is anti-
Bacterium dispersion liquid.
Step 5 prepares silver-loaded silica antiseptic
Under ul-trasonic irradiation, according to actual demand, the silver-loaded silica antibacterial of the high concentration obtained in dilution step 4
Dispersion liquid obtains silver-loaded silica antibacterial dilution, then is added 4% (v/v's) into silver-loaded silica antibacterial dilution
Adhesive obtains silver-loaded silica antiseptic.
Embodiment 3
A kind of preparation method of silver-loaded silica antiseptic, is specifically implemented according to the following steps：
Step 1, the hydrophobic silica colloidal sol for preparing methyl modification
Ethyl orthosilicate (TEOS), dimethyldimethoxysil,ne (DMDMS), absolute ethyl alcohol (EtOH) are placed in ice-water bath
In, stirring 60min makes it be sufficiently mixed for homogeneous phase solution, be slowly added dropwise while stirring homogeneous phase solution distilled water with it is a concentration of
The mixture of the salpeter solution of 2.0mol/L, is stirred and the 5h postcoolings that flow back at 50 DEG C are to room temperature, obtains the hydrophobic of methyl modification
Property silicon dioxide gel, wherein ethyl orthosilicate (TEOS)：Dimethyldimethoxysil,ne (DMDMS)：Absolute ethyl alcohol
(EtOH)：Distilled water：The molar ratio of nitric acid is 1：0.6：10：6：0.10；
Step 2 prepares silver-loaded silica colloidal sol
It is added a concentration of 2.0mol/L's when the hydrophobic silica colloidal sol that the methyl obtained in whipping step 1 is modified
The molar ratio of silver nitrate solution, silver nitrate and ethyl orthosilicate (TEOS) in step 1 is 0.25：1, it has added and has continued to stir
60min；It is subsequently added into 40% (v/v) n,N-Dimethylformamide, is stirred continuously in adding procedure, has been added and continued to stir
60min postcoolings obtain silver-loaded silica colloidal sol to room temperature；
Step 3 prepares silver-loaded silica material
By in step 2 to silver-loaded silica colloidal sol be placed in culture dish, after dry under 60 DEG C of the vacuum environment
It is ground into fine particles, and 450 DEG C is warming up to 5.0 DEG C/min under air or nitrogen atmosphere, roast after 5h again with 3.0 DEG C/min
Cooling down obtains silver-loaded silica material to room temperature；
Step 4, the silver-loaded silica antibacterial dispersion liquid for preparing high concentration
The silver-loaded silica material obtained in step 3 is distributed to the triethanolamine dissolved with 3% (v/v) by step 4.1
(TEA) in distilled water, mixed liquor A is obtained, then mixed liquor A is added to the second of the silane coupling agent KH -560 containing 3% (v/v)
In alcoholic solution, adding procedure is stirred continuously ethanol solution, obtains mixed liquid B；
Step 4.2, the pH value for adjusting mixed liquid B are 9, continue to stir 4h, obtain the silver-loaded silica antibacterial of high concentration
Dispersion liquid.
Step 5 prepares silver-loaded silica antiseptic
Under ul-trasonic irradiation, according to actual demand, the silver-loaded silica antibacterial of the high concentration obtained in dilution step 4
Dispersion liquid obtains silver-loaded silica antibacterial dilution, then is added 5% (v/v's) into silver-loaded silica antibacterial dilution
Adhesive obtains silver-loaded silica antiseptic.
Embodiment 4
A kind of preparation method of silver-loaded silica antiseptic, is specifically implemented according to the following steps：
Step 1, the hydrophobic silica colloidal sol for preparing methyl modification
Ethyl orthosilicate (TEOS), dimethyldimethoxysil,ne (DMDMS), absolute ethyl alcohol (EtOH) are placed in ice-water bath
In, stirring 40min makes it be sufficiently mixed for homogeneous phase solution, be slowly added dropwise while stirring homogeneous phase solution distilled water with it is a concentration of
The mixture of the salpeter solution of 2.0mol/L, is stirred and the 2.5h postcoolings that flow back at 70 DEG C are to room temperature, obtains dredging for methyl modification
Aqueous silica sol, wherein ethyl orthosilicate (TEOS)：Dimethyldimethoxysil,ne (DMDMS)：Absolute ethyl alcohol
(EtOH)：Distilled water：The molar ratio of nitric acid is 1：0.6：10：9：0.04；
Step 2 prepares silver-loaded silica colloidal sol
It is added a concentration of 0.5mol/L's when the hydrophobic silica colloidal sol that the methyl obtained in whipping step 1 is modified
The molar ratio of silver nitrate solution, silver nitrate and ethyl orthosilicate (TEOS) in step 1 is 0.05：1, it has added and has continued to stir
30min；Urea is subsequently added into absolute ethyl alcohol by 1:The urea liquid for a concentration of 0.5mol/L that 1 volume ratio is configured to, urine
The molar ratio of element and silver nitrate is 1:1, it is stirred continuously in adding procedure, has added and continued to stir 30min postcoolings to room temperature, obtained
To silver-loaded silica colloidal sol；
Step 3 prepares silver-loaded silica material
By in step 2 to silver-loaded silica colloidal sol be placed in culture dish, after dry under 30 DEG C of the vacuum environment
It is ground into fine particles, and 450 DEG C is warming up to 5.0 DEG C/min under air or nitrogen atmosphere, roast after 2h again with 3.0 DEG C/min
Cooling down obtains silver-loaded silica material to room temperature；
Step 4, the silver-loaded silica antibacterial dispersion liquid for preparing high concentration
The silver-loaded silica material obtained in step 3 is distributed to the triethanolamine dissolved with 3% (v/v) by step 4.1
(TEA) in distilled water, mixed liquor A is obtained, then mixed liquor A is added to the second of the silane coupling agent KH -560 containing 3% (v/v)
In alcoholic solution, adding procedure is stirred continuously ethanol solution, obtains mixed liquid B；
Step 4.2, the pH value for adjusting mixed liquid B are 9, continue to stir 4h to get anti-to the silver-loaded silica of high concentration
Bacterium dispersion liquid.
Step 5 prepares silver-loaded silica antiseptic
Under ul-trasonic irradiation, according to actual demand, the silver-loaded silica antibacterial of the high concentration obtained in dilution step 4
Dispersion liquid obtains silver-loaded silica antibacterial dilution, then is added 5% (v/v's) into silver-loaded silica antibacterial dilution
Adhesive obtains silver-loaded silica antiseptic.
Embodiment 5
A kind of preparation method of silver-loaded silica antiseptic, is specifically implemented according to the following steps：
Step 1, the hydrophobic silica colloidal sol for preparing methyl modification
Ethyl orthosilicate (TEOS), dimethyldimethoxysil,ne (DMDMS), absolute ethyl alcohol (EtOH) are placed in ice-water bath
In, stirring 30min makes it be sufficiently mixed for homogeneous phase solution, be slowly added dropwise while stirring homogeneous phase solution distilled water with it is a concentration of
The mixture of the salpeter solution of 1.8mol/L, is stirred and the 2h postcoolings that flow back at 75 DEG C are to room temperature, obtains the hydrophobic of methyl modification
Property silicon dioxide gel, wherein ethyl orthosilicate (TEOS)：Dimethyldimethoxysil,ne (DMDMS)：Absolute ethyl alcohol
(EtOH)：Distilled water：The molar ratio of nitric acid is 1：0.45：7：6：0.08；
Step 2 prepares silver-loaded silica colloidal sol
It is added a concentration of 1.5mol/L's when the hydrophobic silica colloidal sol that the methyl obtained in whipping step 1 is modified
The molar ratio of silver nitrate solution, silver nitrate and ethyl orthosilicate (TEOS) in step 1 is 0.25：1, it has added and has continued to stir
50min；Urea is subsequently added into absolute ethyl alcohol by 1:The urea liquid for a concentration of 1.0mol/L that 1 volume ratio is configured to, urine
The molar ratio of element and silver nitrate is 1:1, it is stirred continuously in adding procedure, has added and continued to stir 50min postcoolings to room temperature, obtained
To silver-loaded silica colloidal sol；
Step 3 prepares silver-loaded silica material
By in step 2 to silver-loaded silica colloidal sol be placed in culture dish, after dry under 60 DEG C of the vacuum environment
It is ground into fine particles, and 380 DEG C is warming up to 3.0 DEG C/min under air or nitrogen atmosphere, roast after 3h again with 2.0 DEG C/min
Cooling down obtains silver-loaded silica material to room temperature；
Step 4, the silver-loaded silica antibacterial dispersion liquid for preparing high concentration
The silver-loaded silica material obtained in step 3 is distributed to three ethyl alcohol dissolved with 2.8% (v/v) by step 4.1
In the distilled water of amine (TEA), mixed liquor A is obtained, then mixed liquor A is added to the silane coupling agent KH -560 containing 2.5% (v/v)
Ethanol solution in, adding procedure is stirred continuously ethanol solution, obtains mixed liquid B；
Step 4.2, the pH value for adjusting mixed liquid B are 8, continue to stir 3h, obtain the silver-loaded silica antibacterial of high concentration
Dispersion liquid.
Step 5 prepares silver-loaded silica antiseptic
Under ul-trasonic irradiation, according to actual demand, the silver-loaded silica antibacterial of the high concentration obtained in dilution step 4
Dispersion liquid obtains silver-loaded silica antibacterial dilution, then 3.5% (v/v) is added into silver-loaded silica antibacterial dilution
Adhesive, obtain silver-loaded silica antiseptic.
Embodiment 6
A kind of preparation method of silver-loaded silica antiseptic, is specifically implemented according to the following steps：
Step 1, the hydrophobic silica colloidal sol for preparing methyl modification
Ethyl orthosilicate (TEOS), dimethyldimethoxysil,ne (DMDMS), absolute ethyl alcohol (EtOH) are placed in ice-water bath
In, stirring 60min makes it be sufficiently mixed for homogeneous phase solution, be slowly added dropwise while stirring homogeneous phase solution distilled water with it is a concentration of
The mixture of the salpeter solution of 1.0mol/L, is stirred and the 5h postcoolings that flow back at 50 DEG C are to room temperature, obtains the hydrophobic of methyl modification
Property silicon dioxide gel, wherein ethyl orthosilicate (TEOS)：Dimethyldimethoxysil,ne (DMDMS)：Absolute ethyl alcohol
(EtOH)：Distilled water：The molar ratio of nitric acid is 1：0.3：6：7：0.1；
Step 2 prepares silver-loaded silica colloidal sol
It is added a concentration of 2.0mol/L's when the hydrophobic silica colloidal sol that the methyl obtained in whipping step 1 is modified
The molar ratio of silver nitrate solution, silver nitrate and ethyl orthosilicate (TEOS) in step 1 is 0.10：1, it has added and has continued to stir
60min；Urea is subsequently added into absolute ethyl alcohol by 1:The urea liquid for a concentration of 1.5mol/L that 1 volume ratio is configured to, urine
The molar ratio of element and silver nitrate is 1:1, it is stirred continuously in adding procedure, has added and continued to stir 60min postcoolings to room temperature, obtained
To silver-loaded silica colloidal sol；
Step 3 prepares silver-loaded silica material
By in step 2 to silver-loaded silica colloidal sol be placed in culture dish, after dry under 20 DEG C of the vacuum environment
It is ground into fine particles, and 300 DEG C is warming up to 0.5 DEG C/min under air or nitrogen atmosphere, roast after 5h again with 0.5 DEG C/min
Cooling down obtains silver-loaded silica material to room temperature；
Step 4, the silver-loaded silica antibacterial dispersion liquid for preparing high concentration
The silver-loaded silica material obtained in step 3 is distributed to the triethanolamine dissolved with 2% (v/v) by step 4.1
(TEA) in distilled water, mixed liquor A is obtained, then mixed liquor A is added to the second of the silane coupling agent KH -560 containing 2% (v/v)
In alcoholic solution, adding procedure is stirred continuously ethanol solution, obtains mixed liquid B；
Step 4.2, the pH value for adjusting mixed liquid B are 9, continue to stir 3h, obtain the silver-loaded silica antibacterial of high concentration
Dispersion liquid.
Step 5 prepares silver-loaded silica antiseptic
Under ul-trasonic irradiation, according to actual demand, the silver-loaded silica antibacterial of the high concentration obtained in dilution step 4
Dispersion liquid obtains silver-loaded silica antibacterial dilution, then is added 3% (v/v's) into silver-loaded silica antibacterial dilution
Adhesive obtains silver-loaded silica antiseptic.
Silver-loaded silica antiseptic is characterized to the anti-microbial property of earth's surface water sample with the method for plate culture count, takes implementation respectively
The silver-loaded silica antibacterial dispersion liquid of the high concentration prepared in example 2, embodiment 3, embodiment 4, embodiment 5, is diluted to identical
Concentration adds the adhesive that percent by volume is 5%, does four groups of Duplicate Samples.Take concentration and four groups of Duplicate Samples consistent not again
The silicon dioxide germicide of argentiferous, as blank sample.By five groups of samples after 121 DEG C of autoclave sterilization 30min, add respectively
Enter the Escherichia coli bacteria liquid (dilution 10 of 1mL activation for 24 hours6Times), 18h is vibrated at 25 DEG C of constant temperature water bath, draws 0.1mL in sterilizing
Culture medium on, coating uniformly after, inversion be incubated at 30 DEG C of constant incubator constant temperature incubation 48h after, clump count on plate of making even
Average value is as final result.Wherein sterilizing rate such as Fig. 1 institute of the silver-loaded silica antiseptic to Escherichia coli in earth's surface water sample
Show.
As seen from Figure 1, the sterilization rate of Escherichia coli significantly improves after addition silver, and increases with silver carrying amount, large intestine bar
The sterilization rate of bacterium gradually increases.Illustrate that silver-loaded silica antiseptic has apparent inhibiting effect to the growth of Escherichia coli, and
Silver-colored additive amount is more, and sterilization effect is better.
Claims (10)
1. a kind of preparation method of silver-loaded silica antiseptic, which is characterized in that be specifically implemented according to the following steps：
Step 1, the hydrophobic silica colloidal sol for preparing methyl modification
Ethyl orthosilicate (TEOS), dimethyldimethoxysil,ne (DMDMS), absolute ethyl alcohol (EtOH) are placed in ice-water bath,
30~60min of stirring makes it be sufficiently mixed for homogeneous phase solution, and it is molten with nitric acid that distilled water is slowly added dropwise while stirring homogeneous phase solution
The mixture of liquid, is stirred and 2~5h postcoolings that flow back are to room temperature, obtains the hydrophobic silica colloidal sol of methyl modification；
Step 2 prepares silver-loaded silica colloidal sol
Silver nitrate solution is added when the hydrophobic silica colloidal sol that the methyl that is obtained in whipping step 1 is modified, added after
30~60min of continuous stirring；It is subsequently added into reducing agent, is stirred continuously in adding procedure, has been added cold after continuing 30~60min of stirring
But to room temperature, silver-loaded silica colloidal sol is obtained；
Step 3 prepares silver-loaded silica material
By in step 2 to silver-loaded silica colloidal sol be placed in culture dish, be ground into after drying under vacuum conditions subtle
Grain, and 2~5h is roasted under air or nitrogen atmosphere, obtain silver-loaded silica material；
Step 4, the silver-loaded silica antibacterial dispersion liquid for preparing high concentration
The silver-loaded silica material obtained in step 3 is distributed to dissolved with a certain amount of triethanolamine (TEA) by step 4.1
In distilled water, mixed liquor A is obtained, then mixed liquor A is added in the ethanol solution containing a certain amount of silane coupling agent KH -560, added
Add process to be stirred continuously ethanol solution, obtains mixed liquid B；
Step 4.2, the pH value for adjusting mixed liquid B are 8~9, continue 3~4h of stirring, and the silver-loaded silica for obtaining high concentration is anti-
Bacterium dispersion liquid；
Step 5 prepares silver-loaded silica antiseptic
Under ul-trasonic irradiation, according to actual demand, the silver-loaded silica antibacterial of the high concentration obtained in dilution step 4 is disperseed
Liquid obtains silver-loaded silica antibacterial dilution, then a certain amount of adhesive is added into silver-loaded silica antibacterial dilution, obtains
To silver-loaded silica antiseptic.
2. a kind of preparation method of silver-loaded silica antiseptic according to claim 1, which is characterized in that the step
Ethyl orthosilicate (TEOS) in 1：Dimethyldimethoxysil,ne (DMDMS)：Absolute ethyl alcohol (EtOH)：Distilled water：Nitric acid rubs
You are than being 1：0.3~0.6：6~10：6~9：0.04~0.10.
3. a kind of preparation method of silver-loaded silica antiseptic according to claim 1 or 2, which is characterized in that described
A concentration of 1.0mol/L~2.0mol/L of salpeter solution in step 1, reflux temperature are 50~75 DEG C.
4. a kind of preparation method of silver-loaded silica antiseptic according to claim 1, which is characterized in that the step
Reducing agent in 2 is N,N-dimethylformamide or urea liquid.
5. a kind of preparation method of silver-loaded silica antiseptic according to claim 1, which is characterized in that the step
The molar ratio of silver nitrate and ethyl orthosilicate (TEOS) in step 1 is 0.05~0.25 in 2：1, silver nitrate solution it is a concentration of
0.5mol/L~2.0mol/L.
6. a kind of preparation method of silver-loaded silica antiseptic according to claim 1, which is characterized in that the step
Vacuum drying temperature is 20~60 DEG C in 3, and roasting is to be warming up to 300~450 DEG C with 0.5~5.0 DEG C/min first, roasting 2~
Again with 0.5~3.0 DEG C/min cooling downs to room temperature after 5h.
7. a kind of preparation method of silver-loaded silica antiseptic according to claim 1, which is characterized in that the step
The percent by volume of triethanolamine (TEA) is 2~3% in distilled water in 4, the volume of silane coupling agent KH -560 in ethanol solution
Percentage is 2~3%.
8. a kind of preparation method of silver-loaded silica antiseptic according to claim 1, which is characterized in that the step
The percent by volume that adhesive is added in middle silver-loaded silica antibacterial dispersion liquid is 3~5%.
9. a kind of preparation method of silver-loaded silica antiseptic according to claim 4, which is characterized in that the methyl
The percent by volume of N,N-dimethylformamide is 20~40% in modified hydrophobic silica colloidal sol.
10. a kind of preparation method of silver-loaded silica antiseptic according to claim 4, which is characterized in that the urine
Plain solution is that urea presses 1 with absolute ethyl alcohol:1 volume ratio configures, a concentration of 0.5~1.5mol/L of urea liquid, urine
The molar ratio of element and silver nitrate is 1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810146267.XA CN108385374B (en) | 2018-02-12 | 2018-02-12 | Preparation method of silver-loaded silicon dioxide antibacterial agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810146267.XA CN108385374B (en) | 2018-02-12 | 2018-02-12 | Preparation method of silver-loaded silicon dioxide antibacterial agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108385374A true CN108385374A (en) | 2018-08-10 |
| CN108385374B CN108385374B (en) | 2021-01-08 |
Family
ID=63068879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810146267.XA Active CN108385374B (en) | 2018-02-12 | 2018-02-12 | Preparation method of silver-loaded silicon dioxide antibacterial agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108385374B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110982270A (en) * | 2019-12-25 | 2020-04-10 | 三河市京纳环保技术有限公司 | Silicon-based zinc-loaded antibacterial agent for liquid silicone rubber and preparation method thereof |
| CN111440283A (en) * | 2020-05-29 | 2020-07-24 | 两者时尚商业(江苏)有限公司 | Antibacterial modified polyurethane memory cotton and preparation method thereof |
| CN111607977A (en) * | 2020-05-27 | 2020-09-01 | 同曦集团有限公司 | Antibacterial and antiviral leather and preparation method and application thereof |
| CN111607984A (en) * | 2020-05-27 | 2020-09-01 | 同曦集团有限公司 | Antibacterial and antivirus dye slurry and preparation method and application thereof |
| CN111961403A (en) * | 2020-07-07 | 2020-11-20 | 厦门三德信科技股份有限公司 | Foldable antibacterial transparent hardened layer, antibacterial flexible cover plate and preparation method |
| CN112500722A (en) * | 2020-11-23 | 2021-03-16 | 徐州创合新材料科技有限公司 | Super-hydrophilic long-acting antibacterial glass coating composition and preparation method thereof |
| CN112745601A (en) * | 2020-12-30 | 2021-05-04 | 同曦集团有限公司 | Antibacterial, mildewproof and antiviral material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1623897A (en) * | 2004-11-19 | 2005-06-08 | 中国乐凯胶片集团公司 | Process for preparing silicon dioxide of carrying nano silver |
| CN101171929A (en) * | 2007-10-19 | 2008-05-07 | 无锡汇罗新材料科技有限公司 | Method for preparing nano silver antimicrobials |
| CN101731275A (en) * | 2009-12-29 | 2010-06-16 | 浙江理工大学 | Silicon-zinc nano mesoporous inorganic antibacterial and preparation method thereof |
| CN103039521A (en) * | 2011-10-11 | 2013-04-17 | 国家纳米科学中心 | Method for preparing antibacterial powder loaded with monodisperse silver nanometer mesoporous silica |
| CN104546508A (en) * | 2015-01-19 | 2015-04-29 | 上海交通大学 | Method for preparing nano-silver-based dual-curing dental antibacterial adhesive |
| CN106758176A (en) * | 2016-12-09 | 2017-05-31 | 上海森帝诺体育用品有限公司 | A kind of antiseptic and preparation method thereof |
| CN107189585A (en) * | 2017-06-28 | 2017-09-22 | 福州大学 | A kind of SiO 2 supported nanometer silver water anti-bacteria coating and preparation method thereof |
-
2018
- 2018-02-12 CN CN201810146267.XA patent/CN108385374B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1623897A (en) * | 2004-11-19 | 2005-06-08 | 中国乐凯胶片集团公司 | Process for preparing silicon dioxide of carrying nano silver |
| CN101171929A (en) * | 2007-10-19 | 2008-05-07 | 无锡汇罗新材料科技有限公司 | Method for preparing nano silver antimicrobials |
| CN101731275A (en) * | 2009-12-29 | 2010-06-16 | 浙江理工大学 | Silicon-zinc nano mesoporous inorganic antibacterial and preparation method thereof |
| CN103039521A (en) * | 2011-10-11 | 2013-04-17 | 国家纳米科学中心 | Method for preparing antibacterial powder loaded with monodisperse silver nanometer mesoporous silica |
| CN104546508A (en) * | 2015-01-19 | 2015-04-29 | 上海交通大学 | Method for preparing nano-silver-based dual-curing dental antibacterial adhesive |
| CN106758176A (en) * | 2016-12-09 | 2017-05-31 | 上海森帝诺体育用品有限公司 | A kind of antiseptic and preparation method thereof |
| CN107189585A (en) * | 2017-06-28 | 2017-09-22 | 福州大学 | A kind of SiO 2 supported nanometer silver water anti-bacteria coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杨靖等: "Ag/SiO2抗菌材料的制备及抗菌性能研究", 《材料导报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110982270A (en) * | 2019-12-25 | 2020-04-10 | 三河市京纳环保技术有限公司 | Silicon-based zinc-loaded antibacterial agent for liquid silicone rubber and preparation method thereof |
| CN110982270B (en) * | 2019-12-25 | 2024-08-13 | 三河市京纳环保技术有限公司 | Silicon-based zinc-loaded antibacterial agent for liquid silicone rubber and preparation method thereof |
| CN111607977A (en) * | 2020-05-27 | 2020-09-01 | 同曦集团有限公司 | Antibacterial and antiviral leather and preparation method and application thereof |
| CN111607984A (en) * | 2020-05-27 | 2020-09-01 | 同曦集团有限公司 | Antibacterial and antivirus dye slurry and preparation method and application thereof |
| CN111607977B (en) * | 2020-05-27 | 2023-03-10 | 同曦集团有限公司 | Antibacterial and antiviral leather and preparation method and application thereof |
| CN111440283A (en) * | 2020-05-29 | 2020-07-24 | 两者时尚商业(江苏)有限公司 | Antibacterial modified polyurethane memory cotton and preparation method thereof |
| CN111961403A (en) * | 2020-07-07 | 2020-11-20 | 厦门三德信科技股份有限公司 | Foldable antibacterial transparent hardened layer, antibacterial flexible cover plate and preparation method |
| CN112500722A (en) * | 2020-11-23 | 2021-03-16 | 徐州创合新材料科技有限公司 | Super-hydrophilic long-acting antibacterial glass coating composition and preparation method thereof |
| CN112745601A (en) * | 2020-12-30 | 2021-05-04 | 同曦集团有限公司 | Antibacterial, mildewproof and antiviral material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108385374B (en) | 2021-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108385374A (en) | A kind of preparation method of silver-loaded silica antiseptic | |
| CN109788760B (en) | Antimicrobial photoreactive compositions comprising organic and inorganic multijunction composites | |
| US20190000745A1 (en) | Polymer-based antimicrobial compositions and methods of use thereof | |
| CN101273729B (en) | Fungal spore oil suspending agent | |
| CN107326470B (en) | A kind of processing method of the lasting modified polyester fiber of antibacterial | |
| CN103741451A (en) | Antibacterial asthma-resisting quilt cover fabric production process | |
| KR101732276B1 (en) | Whole cloth radiating far-infrared ray and manufacturing process thereof | |
| CN107604662B (en) | Sterilizing and anti-virus composition for finishing textiles | |
| CN109260222A (en) | Cysteine base antimicrobial nano vulcanizes iron mixture and its preparation method and application | |
| CN102839535A (en) | Manufacturing method of durable composite antibacterial textile | |
| CN110496219A (en) | A kind of synthetic method of novel ferrihydrite nanometric photosensitizer and its application in anticancer antibiotic | |
| CN104521989A (en) | Compound composition containing 2-(p-fluorophenyl)-5-methanesulfonyl-1,3,4-oxadiazole and amide bactericides and preparation | |
| CN107660557A (en) | A kind of bactericidal composition containing bacillus amyloliquefaciens and Difenoconazole | |
| CN104666100A (en) | Novel daily cosmetic antibacterial and antiseptic material and application thereof | |
| CN102851768A (en) | Production method of durable composite antibiotic fibers | |
| CN102648713B (en) | Technology for improving biological disease-prevention activity of trichoderma preparation by utilizing fungi activator protein | |
| CN107568265A (en) | A kind of silver-colored copper-rare earth compound antimicrobial agent of plastics | |
| CN101747008B (en) | Plastering mortar material and preparing method thereof | |
| CN106614671B (en) | Mosquito repellent liquid and preparation method thereof | |
| CN107669508A (en) | A kind of preparation technology of antibacterial wet tissue | |
| CN107524000A (en) | A kind of preparation method of natural antibacterial mite-assistant fabricses coating | |
| CN107087640A (en) | A kind of bactericidal composition and its application containing bacillus amyloliquefaciens and Prochloraz | |
| CN111514181B (en) | Antibacterial composition, antibacterial composite nano-particles, preparation method of antibacterial composite nano-particles and targeted slow-release nano-private gel | |
| WO1999020105A1 (en) | A porous forming article for eliminating harmful microorganisms and a process of producing it | |
| CN103783078B (en) | A kind of zinc hydroxyl stannate/CMC hydridization antibacterial agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |