CN110144150A - Antibacterial barrier coat compositions and preparation method thereof for medical inspection platform - Google Patents
Antibacterial barrier coat compositions and preparation method thereof for medical inspection platform Download PDFInfo
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- CN110144150A CN110144150A CN201910405126.XA CN201910405126A CN110144150A CN 110144150 A CN110144150 A CN 110144150A CN 201910405126 A CN201910405126 A CN 201910405126A CN 110144150 A CN110144150 A CN 110144150A
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- 150000003904 phospholipids Chemical class 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004393 prognosis Methods 0.000 description 1
- HODRTCMDYBNYNH-UHFFFAOYSA-N propan-2-one;prop-2-enoic acid Chemical compound CC(C)=O.OC(=O)C=C HODRTCMDYBNYNH-UHFFFAOYSA-N 0.000 description 1
- MQVMJSWYKLYFIG-UHFFFAOYSA-N propane-1-sulfonic acid;sodium Chemical compound [Na].CCCS(O)(=O)=O MQVMJSWYKLYFIG-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- UWSCPROMPSAQOL-UHFFFAOYSA-N trimethylazanium;sulfate Chemical compound CN(C)C.CN(C)C.OS(O)(=O)=O UWSCPROMPSAQOL-UHFFFAOYSA-N 0.000 description 1
- 238000005353 urine analysis Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The present invention relates to a kind of antibacterial barrier coats for medical inspection platform into film liquid and preparation method thereof, it is described to contain Solid micro at film liquid, it include: loading nano silvery-titanium dioxide silica solution component, the organically-modified mesoporous silicon oxide antibacterial composite microsphere component of doping nano-Ag, compound organic resin component, hexamethylene or phosphate and other adjuvant components.The antibacterial barrier coat of the present invention can be used for the surface filming isolation purposes that hospital inspection platform for example examines the various work of department or operating table surface, utensil access bracket or working cabined at film liquid, have excellent disinfecting, antimicrobial and hydrophobic function easy to clean.
Description
Technical field
The invention belongs to medical composite material fields, and in particular to a kind of antibacterial particle deposition compound resin containing nano silver
Emulsion-type coating filming liquid composite and preparation method thereof.
Background technique
Medical test is clinical and preclinical medicine bridge, including clinical chemistry, microculture, immunology, hematology
And a variety of subjects such as body fluid blood, it is related to biochemical analysis, immunologic test and microorganism checking etc..Medical test examines clinic
Break, judge that curative effect and prognosis have highly important effect.
In hospital, medical test usually carries out microbiology, immunology, biochemistry, something lost to the material for being derived from human body
The culture and inspection for passing, hematology, biophysics, cytology etc., are related to the inspection of disposable test instrument, patient
Survey body fluid and tissue sample, bacterial virus of culture etc..Such as urine examination and excrement are examined, and are a kind of detection mode of medicine, urine examination
Including urine analysis of blood, formation in urine detection, protein ingredient quantitative determination, urine enzymatic determination etc..Due to detecting
The samples such as body fluid and blood or sample waste object will inevitably pass through various operating platforms such as work top, various in journey
Test tube or appliance stand carry out, and are easy to bring germ contamination；Especially sample or reagent when shaking or shake occur in operation
Slight splash out is more easier that operating platform is caused to pollute；But operating platform used in current inspection department does not have antibiotic and sterilizing
Function, cleaning be easy to cause bacterium mass propagation in platform surface especially edge not in time or when being not thorough, to work
Personnel health has an adverse effect；In addition, current table top does not have hydrophobicity usually, liquid is from suction pipe during checked operation
With lead to operating platform surface contamination when ease is spilt once in a while in sampling container and be not easily cleaned or clean.Therefore, it is necessary to develop use
In the antibacterial barrier coat of medical inspection platform spraying, to reach effectively antibacterial and isolation purposes.
Anti-biotic material containing metal ion is widely noticed because of its potential is worth.Wherein silver-ion antibiotic effect is than it
His metal ion is good, is usually supported on the substance with good mechanical properties and porous three-dimensional structure, to improve its property
Energy.Titanium dioxide is a big important component of inorganic antibacterial material.The growth of bacterium and breeding need organic nutrient substance, and two
The activity hydroxy that titanium oxide photochemical catalyst generates can decompose these organic nutrient substances, inhibit bacterium enhancing and development, thus very big
Reduce bacterial number in degree, achievees the purpose that antibacterial and sterilization.
In the prior art, CN201811506925 discloses material surface coating technique field, is related to a kind of space mechanism
High-bond solid antimicrobial lubricant film layer and preparation method thereof.It specifically include matrix, Ti binder course, TiN transition zone, TiN function
Layer, MoS2-Cu-Ag functional layer, the nanocrystalline composite coating successively constituted；Wherein, TiN functional layer and MoS2-Cu-Ag functional layer
It is alternately arranged, and outermost layer is MoS2-Cu-Ag functional layer.Although preparing nanocomposite film layer tool prepared by the patent
There is antibiotic property, but adhesive force is too strong to be not easy to take off film removing.CN201811167499 discloses a kind of anti-bacterial packaging film, raw material
It is grouped as by the group of following parts by weight: 110~140 parts of linear low density polyethylene (LLDPE), ethylene-vinyl acetate copolymer 30~50
Part, 25~40 parts of ethylene-vinyl alcohol copolymer, 20~30 parts of polyvinyl alcohol, silver nitrate and 8~18 parts of zinc oxide mix, two
3~7 parts of titanium oxide, 5~15 parts of kaolin, 12~16 parts of glass fibre, 14~19 parts of plasticizer, although which has
Antibacterial effect, but be not suitable for medical platform environment spraying film forming, it can only be used to finished film laying, poor adhesive force.
CN201811642361 discloses a kind of liposome/chitosan anti-bacteria, antioxygen for embedding laurin oil and nano silver
Change coating liquid preparation method and application, use lignin be reducing agent prepare lignin coat nano silver antimicrobials, and with
Natural phospholipid or synthetic phospholipid, cholesterol are lipid bilayer matrix, and oil-soluble laurin oil is anti-oxidant reinforcing agent, with wood
The nano silver antimicrobials of quality cladding are compound, and the multi-functional liposome of embedding laurin oil and nano silver is prepared；Then should
Multi-functional liposome is mixed with chitosan solution, and the coating liquid is prepared.However the anti-oxidant coating liquid intensity of the invention
And poor adhesive force, it is only applied to food packaging, there is good lasting antioxidation and antibacterial action.
CN201811231185 discloses a kind of polylactic acid-polypyrrole composite antibacterial thin films and preparation method thereof.This poly- cream
Acid-polypyrrole composite antibacterial thin films include that the antibacterial of polylactic acid film and uniform fold on the polylactic acid film surface applies
Layer, the antimicrobial coating are the polypyrrole that pyrrole monomer is formed in the polylactic acid film surface aggregate.This antibacterial film is only fitted
It uses, can not be used in body surface film for forming a film.
CN201811275068 discloses a kind of clothes antibiotic property thermoplastic polyurethane nethike embrane and preparation method, by following
The raw material of mass parts is prepared: 20~40 parts of isocyanates, 50~80 parts of polyester polyol, 4~12 parts of chain extender, compound anti-
10~15 parts of microbial inoculum, 0.005~0.05 part of catalyst, 0.2~2 part of additive, the complex antimicrobials are chitosan-Ag network
Close object.Using chitosan-Ag complex compound as complex antimicrobials, preparation process is cumbersome for the invention, is suitable only for finished film use.
In addition, the prior art also disclose it is a series of for weaving or the film forming agent of clothing purposes.Such as
CN201811357446, which is disclosed, changes a nanometer property tourmaline powder/origanum oil extracting solution-latex antibacterial film preparation method, comprising:
Modified verdelite powder and origanum oil extracting solution are prepared, then by Heveatex, origanum oil extracting solution, vulcanizing ingredient and modified electricity
Gas mountain flour carries out reacting obtained modified Nano tourmaline powder/origanum oil extracting solution-Heveatex multiple emulsion, finally by Composite Milk
Liquid, which is poured into, carries out drying and forming-film on the glass plate with frame, gained dry film is put into progress after cure experiment in vacuum oven
It can be prepared by the antibacterial film.CN103710970 discloses a kind of clothing degerming and deoils modification finishing agent, quality percentage
Than composition are as follows: the hydroxypropyl methyl cellulose of 6-7%, the life of amine-terminated hyperbranced compound the quaternary ammonium HBP-HTC, 3-4% of 8-9%
Object enzyme, the sodium benzoate of 1-3%, the algal polysaccharides analog derivative of 7-8%, the polybasic carboxylic acid finishing agent of 2-3%, the coconut palm of 2-4%
Seed oil fatty monoethanol amide, β-chitosan quaternary ammonium hyaluronic acid derivatives of 7-8%, the dodecyl of 10-15%
Trimethyl ammonium sulfate, the triethanolamine of 5-6%, the deionized water of surplus.CN105926279 is arranged for a kind of wrinkle resistant antibacterial clothes
Agent and application method, including 5-8 parts of Blumea oil, it 25-35 parts of chitosan, 55-65 parts of aqueous polyurethane, 12-18 parts of softening agent, seeps
Saturating JFC3-6 parts of agent, 2-8 parts of catalyst.CN103103789 discloses a kind of preparation method of blood-resistant clothing finishing agent, including
Following processing step: 1) 9 parts by weight of ammonium polyphosphate, 78 parts by weight of fluorocarbon resin, 7 parts by weight of zirconium carbide, 6 weight of titanium dioxide are taken
Part, then mixing is added 100 parts by weight of deionized water, pours into emulsion tank and emulsified；2) reaction kettle is instilled after emulsifying
In, while two fourth of 2 parts by weight of cycloaliphatic polyisocyanate, 6 parts by weight of dodecafluoroheptyl methacrylate and tin dilaurate is added dropwise
0.3 parts by weight of base tin, time for adding are 2.5 hours, and temperature control is at 72~75 DEG C during dropwise addition；3) after being added dropwise to complete, 72
~75 DEG C keep the temperature 1 hour, are then cooled to 35 DEG C；4) nanofiltration device filtering is carried out, nanoscale finishing agent product is obtained.Above-mentioned hair
For bright product although can be used for the fabric surface treatments such as clothing, thermal stability and mechanicalness are poor, are not suitable for medical inspection
Test the surface treatment purposes such as the film isolation of platform.
Therefore, it is necessary to develop, low with toxicity, platform surface compatibility is good, easily take off film and is not easy the spies such as imbibition is contaminated
The film product of point, and there is stronger biocidal property and mechanical performance, every purposes suitable for medical inspection environment.
Summary of the invention
To overcome the medical inspection purposes barrier coat for lacking in the prior art and there is good physical and biocidal property, this
Invention provides a kind of antibacterial barrier coat compositions and preparation method thereof for the processing of medical inspection platform surface, party's legal system
Antibacterial particle and film forming compound resin component, preparation process of the composition containing loading nano silvery obtained is simple.
Specifically, on the one hand, the present invention provides a kind of antibacterial barrier coat for medical inspection platform into the system of film liquid
Preparation Method, the coating are the emulsion form containing Solid micro at film liquid, including: loading nano silvery-titanium dioxide
Silica solution component, the organically-modified mesoporous silicon oxide antibacterial composite microsphere component of doping nano-Ag, compound organic resin group
Point, hexamethylene or phosphate and other auxiliary agents.
The auxiliary agent includes the helper components such as silane coupling agent, surfactant and pH adjusting agent.
Wherein, the organically-modified mesoporous silicon oxide antibacterial complex microsphere of the loading nano silvery and compound organic resin are logical
Lotion cladding is crossed to be organically combined.The present invention is organically-modified by carrying out to mesoporous silicon oxide, overcomes meso-porous titanium dioxide
The weak drawback of silicon particle loading nano silvery ability keeps nano-Ag particles joint efficiency higher more stable；Simultaneously using compound organic
Resin wraps up silica antibacterial complex microsphere, and antibacterial complex microsphere is made to form core with molecular resin in the course of the polymerization process
Shell structure is distributed more uniform.Finally, under the action of silane coupling agent, so that loading nano silvery-titanium dioxide silica solution
Can effectively be combined closely resin micelle surface, thus the antibacterial barrier coat lotion that forming properties are stable.Through the invention
Your preparation method, coating film forming is in use, the antibacterial granules such as nano silver not only may be uniformly distributed in inside film, silica solution
In nano silver and have the active nano-titanium dioxide of photocatalysis antibacterial can also be uniformly distributed in film surface.
To achieve the above object, the present invention uses following technical scheme.
A kind of antibacterial barrier coat for medical inspection platform at film liquid preparation method, the coating at film liquid be containing
There is the emulsion form of Solid micro, including: loading nano silvery-titanium dioxide silica solution component, doping nano-Ag
Organically-modified mesoporous silicon oxide antibacterial composite microsphere component, compound organic resin component, hexamethylene or
Phosphate and other auxiliary agents, preparation include the following steps S1-S6:
S1: nano silver-titanium dioxide silica sol liquid is prepared；
S2: organically-modified mesoporous silicon oxide-nanometer silver antimicrobial complex microsphere is prepared；
S3: antibacterial complex microsphere-polyvinyl alcohol dispersion liquid is prepared using the antibacterial complex microsphere in step S2；
S4: compound organic resin uniformly coats the antibacterial microballoon；
S5: resin emulsification system base fluid is prepared；
S6: base fluid is compounded with silica solution dispersion liquid, and cosmocil stearate is added, and obtains antibacterial barrier coat film forming
Liquid.
Specifically, above-mentioned each specific steps operation is as follows.
Step S1: nano silver-titanium dioxide silica sol liquid is prepared
Under the conditions of being protected from light, stabilizer is added into silver nitrate solution, stirs, reducing agent sodium borohydride solution is then added dropwise,
It is stirred when being added dropwise, after completion of dropwise addition, continues magnetic agitation 2-6h, obtain clear and bright Nano silver solution；
Appropriate above-mentioned Nano silver solution is taken, is slowly added dropwise to the 5-10% silica sol liquid of 10-20 times of volume (silica point
Dispersion liquid) in, it is uniform to be protected from light ultrasonic disperse；
3) under the conditions of 30-35 DEG C of bath temperature and magnetic agitation, a certain amount of nano-titanium dioxide is added and continues to be protected from light
Stirring 2-6 hours, obtains loading nano silvery-titanium dioxide silica solution.
Wherein, silver nitrate solution concentration described in step 1) is 1-2mM；The sodium borohydride solution is 5-20mM, preferably
10-20mM。
Wherein, the dosage of nano-titanium dioxide is the 1-10wt% of silicone content in solution.
Step S2: organically-modified mesoporous silicon oxide-nanometer silver antimicrobial complex microsphere is prepared
1) organically-modified mesoporous silicon dioxide micro-sphere preparation: taking meso-porous titanium dioxide Si powder and appropriate organic modifiers,
It is scattered in distilled water respectively, two kinds of dispersion solution is heated to 60 DEG C and are mixed, DMF solvent and silane coupled is added
After 1-3h is stirred in agent, vacuum pump is filtered, and filter cake is cleaned with deionized water, and it is micro- to obtain organically-modified silica for drying and grinding
Ball；Wherein, grinding control microspherulite diameter is within 100nm.
Wherein, the preferred polyvinylpyrrolidone of the organic modifiers (PVP).
2) in the reaction unit equipped with stirring and thermometer, by the improved silica aqueous microsphere of 10-100mg/ml
Dispersion liquid and appropriate AgNO3Solution mixing is protected from light stirring 1-5h at room temperature, the sodium borohydride solution of proportional quantities is then added dropwise, in
0-10 DEG C is continued to stir 1-3h, and after reaction, the complex microsphere dispersion liquid of preparation is centrifuged, and discards supernatant liquid, solid dispersion
Into water, organically-modified mesoporous silicon oxide-nanometer silver antimicrobial complex microsphere, repeated centrifugation, the process of dispersion 1-2 times are obtained
To purify antibacterial complex microsphere.
Preferably, the reaction condition of above-mentioned steps S2 is as follows:
1) 5-10g meso-porous titanium dioxide Si powder and 1-5g polyvinylpyrrolidone organic modifiers are taken, is scattered in respectively
In 100ml distilled water, two kinds of solution are heated to 50-60 DEG C and are mixed, 30-80ml DMF solvent and 0.5-2g is added
After triethoxysilane coupling agent stirs 1-3h, vacuum pump is filtered, and filter cake is cleaned with deionized water, drying and grinding, is obtained organic
Modified silicon dioxide microsphere particle controls partial size 20-100nm.
2) in the reaction unit equipped with stirring and thermometer, by the improved silica aqueous microsphere of 10-100mg/ml
Dispersion liquid and appropriate AgNO3Solution mixing is protected from light stirring 1-5h at room temperature, the sodium borohydride solution of proportional quantities is then added dropwise, in
0-10 DEG C is continued to stir 1-3h, and after reaction, the complex microsphere dispersion liquid of preparation is centrifuged, and discards supernatant liquid, solid dispersion
Into water, obtain the organically-modified mesoporous silicon oxide antibacterial complex microsphere of loading nano silvery, repeated centrifugation, the process of dispersion with
Purify antibacterial complex microsphere.
Step S3: antibacterial complex microsphere polyvinyl alcohol dispersion liquid is prepared
At 60-65 DEG C, resulting antibacterial complex microsphere is added in the polyvinyl alcohol clear solution of 1-5wt%, magnetic
Power stirs 30-60min, and then ultrasonic vibration disperses 10-15min, after ultrasonic vibration again magnetic agitation 30-60min to get anti-
Bacterium particle dispersion liquid；Wherein, the mass percent of antibacterial microballoon is 10-20% in antibacterial complex microsphere dispersion liquid.
Preferably, the mass percent of antibacterial microballoon is 10-15% in antibacterial complex microsphere dispersion liquid.
It is highly preferred that the mass percent of antibacterial microballoon is 10-12%.
Step S4: compound organic resin coats antibacterial microballoon
1) PVDF (Kynoar) particle is added in DMF solvent, is stirred 1-3h under 60 DEG C of waters bath with thermostatic control and obtains
Mass percent is the PVDF solution of 20-30%；It is the polyacrylate acetone soln of 15-20% and above-mentioned by mass fraction
PVDF solution 1:0.5-1 in mass ratio mixing, it is 0.5-1% that pore-foaming agent to mass fraction, which is added, stirs evenly and is compounded with to obtain the final product
Machine resin solution.
Wherein, the polyacrylate is selected from polymethyl acrylate, polyethyl acrylate, polyacrylic acid propyl ester or polypropylene
The polyalkyl acrylates such as acid butyl ester, preferably polymethyl acrylate.
Optionally, appropriate aqueous polyurethane can also be added, be selected from polyether-type or polyester-type aqueous polyurethane.
Wherein, the perforating agent is selected from polyvinylpyrrolidone.
2) low whipping speed is 200-500r/min and under conditions of temperature is 50 DEG C~60 DEG C, and above-mentioned antibacterial is compound micro-
Ball dispersion liquid is in being slowly added into compound resin solution, then low whipping speed is 300-500r/min and temperature is 50 DEG C~60
2-6h is stirred at DEG C；Ultrasonic vibration 15-20min removes bubble.
Wherein, antibacterial complex microsphere dispersion liquid and compound resin solution quality amount ratio are 1:1-5；It is added to compound resin
Feed way in solution, which is preferably added dropwise, to be added, it is preferable that feed time 0.5-1h.
Step S5: emulsification system base fluid is prepared
In the reaction unit equipped with stirring and condensation, polymerisable surfactant solution is slowly added into 50-55 DEG C
Deaeration resin mixture liquor in, control be added polymerisable surfactant mass fraction be 1-3wt%；Surpass after stirring 0.5-1h
Sound wave emulsifies to obtain emulsification system base fluid, ultrasonic power 200-500W, time 10-20min.
Wherein, the polymerisable surfactant is selected from sodium maleic monododecylamide propylsulfonate or allyloxy nonyl benzene
Oxygroup propyl alcohol polyoxyethylene ether.
Preferably, polymerisable surfactant mass fraction is 10-25%.
Step S6: antibacterial barrier coat is prepared into film liquid
Under the conditions of insulated and stirred, the silicon sol solution of above-mentioned loading nano silvery-titanium dioxide is slowly added into above-mentioned cream
In change system, feed time is controlled in 0.5h；It feeds and silane coupling agent is added to 0.5-2wt% to mixed liquor after finishing, protect
Temperature stops heating after being stirred to react 1-2h, is down to room temperature, appropriate hexamethylene or phosphate is added to 10-
50mg/L adjusts pH to 7-7.6, is sealed；Up to the antibacterial barrier coat at film liquid.
Wherein, the mass ratio of emulsification system and silicon sol solution is 1:0.1-0.5.
Wherein, the silane coupling agent preferably is selected from triethoxy alkyl silane coupling agent, such as triethoxy octyl silane.
Wherein, the pH is adjusted is adjusted using ammonium hydroxide.
Wherein, hexamethylene or phosphatic mass fraction are preferably 10-30mg/L.
Antibacterial barrier coat emulsion solid content obtained by the present invention is about 10-25%, and colloidal particles particle size is 80-
200nm, storage-stable, form a film 350% or more elongation at break, and 72 hours common to Escherichia coli, gold-coloured staphylococci etc.
The sterilizing rate of bacterium reaches 95% or more.
Coating of the present invention is colorless and transparent film after drying at room temperature or heated-air drying at film liquid.
On the other hand, the present invention provides antibacterial barrier coat made from the preparation method into film liquid or coated film.
The antibacterial barrier coat of the present invention can be used for hospital inspection platform at film liquid and for example examine the various work of department or operation
The surface coating purposes of table top, utensil access bracket or working cabined, has disinfecting, antimicrobial and hydrophobic function easy to clean.
Typical spray known in the art or coating method can be used in the coating method, and thickness can be according to practical operation
Platform situation appropriate adjustment, such as can be 0.01-0.5mm.
In addition, when the antibacterial barrier coat lotion of the present invention is used for protective garment or emgloves spraying use, it can be with suitably
Organic solvent or water futher stir dilution 3-5 times carry out it is canned, assembly aerosol valve simultaneously seal, then fill diformazan ethers throw
Penetrate agent.
Compared with prior art, the invention has the following beneficial effects:
(1) product of the present invention has excellent antibacterial effect and mechanical performance.Nano silver is divided into two parts, so that applying
Layer surface and inside can be uniformly distributed.A portion is supported on changing with good mechanical performance and porous three-dimensional structure
On property meso-porous titanium dioxide silicon components, another part and nano-titanium dioxide are supported on colloidal sol silicon components, pass through silane coupling agent
Can integrated distribution in coating surface so that film forming coatings also have titanium dioxide while discharging silver ion under excited by visible light
The photocatalysis antibacterial activity of titanium.Compound resin based on PVDF and polyacrylate is that have fabulous chemical stability, thermostabilization
Property, mechanical performance polymer, have compared with strong-hydrophobicity, it is not easy to by operating platform liquid pollute, improve its pollution resistance,
And easy to clean.
(2) nano-titanium dioxide in composition has the synergistic effect between inorganic silver ion, effectively enhances painting
The antibacterial action of layer.On by the operating platform of the pollutions such as body fluid, blood or culture solution, the growth and breeding of bacterium need these
Organic nutrient substance, and the activity hydroxy that optically catalytic TiO 2 generates has high reaction energy, can decompose rapidly these has
Machine nutrients inhibits bacterial multiplication to achieve the purpose that Synergistic antimicrobial and sterilization to effectively reduce bacterial number.Meanwhile
Itself also has very strong mould proof effect.Importantly, examining department to usually require to carry out ultraviolet disinfection, therefore even if not having
Have compared under conditions of intense light irradiation, can also photo-catalyst be excited to react by ultraviolet light titanium dioxide.
(3) the modified mesoporous silicon oxide composite antibacterial microballoon of the present invention by be modified mesoporous silicon oxide, nano silver it is compound and
There is porous structure and large specific surface area at, mesoporous silicon oxide, there is very strong adsorptivity after organically-modified, nano silver
Grain surface synthesis composite antibacterial particulate microsphere easy to attach.The particle can effectively enhance the antibacterial bacteriostatic performance of film forming coatings, together
When avoid nano-Ag particles be easy reunite defect, good dispersion；It can additionally by the operations such as polymeric surfactant are added
It further prevents nano silver to reunite, further enhances dispersion performance.
(4) present invention high-molecular resin solution compound with polyacrylate and PVDF has good after film forming is dry
Hydrophobicity, Physical Mechanical and toughness.Antibacterial microballoon dispersion liquid is mixed with high-molecular resin solution, so that antibacterial particle is molten
It is easier to mix in liquid, is easy to be uniformly distributed in molding coating, while the mechanical property of coated film can also be effectively improved.
(5) present invention is by silica inorganic particulate component in conjunction with high molecular polymer, additionally it is possible to improve compound organic
The thermal stability of polymer material.Meanwhile wherein nano silver also can be improved in organic polymer and antibacterial agent poly hexamethylene biguanide
The stability of component.Nano-ag composite is compatible with organic polymer matrix, the even particle size distribution at film liquid and coating, point
It is good to dissipate property, so that the antibacterial effect of nano silver is obviously improved.Preparation method is simple, greatly reduces production difficulty, convenient
Antimicrobial coating/film surface treatment for various platform materials.
(6) of the invention to play the role of being effectively isolated pollutant at coating made of film liquid, in addition to antibacterial bacteriostatic
Effect also has preferable hydrophobicity, plays the effect of waterproof liquid-proof, be not easy to be infected with spot, also have extensively in other devices fields
General application prospect.
(7) preparation method of the invention is simple and convenient, is suitble to large-scale production.
Specific embodiment
Below by specific preparation example and embodiment, the present invention is described in detail, but these exemplary embodiments
Purposes and purpose be only used to enumerate the present invention, any type of any limit not is constituted to real protection scope of the invention
It is fixed, it is more non-that protection scope of the present invention is confined to this.
The detailed description of preferred implementation method of the invention below and including embodiment can be more easily to understand it is of the invention
Content.Unless otherwise defined, all technologies used herein and scientific term have and fields ordinary skill of the present invention
The normally understood identical meaning of personnel.When there is a conflict, the definition in this specification shall prevail.
Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that covering
Non-exclusionism includes.For example, composition, step, method, product or device comprising listed elements are not necessarily limited to those and want
Element, but may include not expressly listed other elements or such composition, step, method, product or device it is intrinsic
Element.
Preparation example 1
Prepare loading nano silvery-titanium dioxide silica solution
1) 17.0mg silver nitrate is weighed, 100ml deionized water dissolving is added to be configured to the silver nitrate solution of 1mmol/L, will be matched
The silver nitrate solution of system is kept in dark place in brown volumetric flask.The above-mentioned silver nitrate solution of 60ml is taken to be placed in the taper with stirrer anti-
Bottle is answered, the sodium citrate solution of 9ml 40mM is added as stabilizer, 5min is stirred, then under the conditions of quickly stirring and being protected from light
The 10mM sodium borohydride solution of 6ml is added dropwise, is stirred when being added dropwise, continues magnetic agitation 3h after completion of dropwise addition, obtains clear and bright nanometer
Silver-colored solution.
2) the above-mentioned Nano silver solution for taking 50mL is slowly added dropwise to 10% silica sol liquid of 600g (silica dispersions)
In, it is protected from light, ultrasonic disperse is uniform.
3) nano-titanium dioxide 1.2g is weighed, under the conditions of 30 DEG C of bath temperatures and magnetic agitation, above-mentioned silica solution is added
In liquid, ultrasonic disperse is uniform, continues to be protected from light stirring 4 hours, obtains loading nano silvery-titanium dioxide silica solution.
Preparation example 2
Prepare organically-modified mesoporous silicon oxide-nanometer silver antimicrobial complex microsphere
1) 10g meso-porous titanium dioxide Si powder and 3g polyvinylpyrrolidone organic modifiers are taken, is scattered in 100ml steaming respectively
In distilled water, two kinds of solution are heated to 60 DEG C and are mixed, 50ml DMF solvent is added and 0.5g triethoxysilane is even
After joining agent stirring 2h, vacuum pump is filtered, and filter cake is cleaned with deionized water, and drying and grinding obtains organically-modified to 80nm is no more than
Silicon dioxide microsphere.
2) in the reaction unit equipped with stirring and thermometer, the organically-modified silica of 200ml 50mg/ml is micro-
The AgNO of ball aqueous dispersions and 10ml 10mM3Solution mixing is protected from light stirring 2h at room temperature, is then added dropwise under agitation
5ml 20mM sodium borohydride solution continues to stir 2h in 5 DEG C after being added dropwise；After stirring, by the complex microsphere of preparation point
Dispersion liquid is centrifuged 20min, removes supernatant, solid is distributed in deionized water, obtains nano silver/organically-modified mesoporous silicon oxide
Complex microsphere crude product, repeated centrifugation, dispensing laundry process are to purify antibacterial complex microsphere.
Preparation example 3
Prepare antibacterial complex microsphere polyvinyl alcohol dispersion liquid
At 60 DEG C, the resulting antibacterial complex microsphere of preparation example 2 is added to the polyethylene of a certain amount of 3wt% mass fraction
In alcohol clear solution, magnetic agitation 60min, then ultrasonic vibration disperses 15min, magnetic agitation 60min again after ultrasonic vibration,
Up to antibacterial particle dispersion liquid, wherein so that the mass percent of antibacterial microballoon is 12% in antibacterial complex microsphere dispersion liquid.
Preparation example 4
Compound organic resin coats antibacterial microballoon
1) PVDF particle is added in DMF solvent, is stirred 2h under 60 DEG C of waters bath with thermostatic control to obtain mass percent
For 25% PVDF solution；The polymethyl acrylate acetone soln 1kg and PVDF solution 0.5kg for being 20% by mass fraction is abundant
It is stirred, it is 1% that pore-foaming agent polyvinylpyrrolidone to mixed liquor mass fraction, which is added, continues to be stirred until homogeneous to be compounded with
Machine resin solution.
2) low whipping speed is 300r/min and under conditions of temperature is 60 DEG C, by above-mentioned antibacterial complex microsphere dispersion liquid
0.5kg is slowly added into the 1kg compound resin solution of above-mentioned preparation, feed time 0.5h, then low whipping speed is 400r/
Min and temperature are to continue to be stirred 3h at 60 DEG C；Ultrasonic vibration 15min after stirring stands removing bubble.
Embodiment 1
Antibacterial barrier coat is prepared into film liquid
1) in the reaction unit equipped with stirring and heating condensation, by the surfactant maleic acid list 12 of concentration 25%
Amine propyl sulfonic acid sodium solution is slowly added into 55 DEG C of deaeration resin mixture liquor of the above-mentioned preparation of 1kg, so that table in mixed liquor
Face activating agent final mass score is 1.5wt%；0.5h is quickly stirred after charging, and cream is then obtained using ultrasonic emulsification
Change system base fluid, ultrasonic power 300W, time 10min.
2) under the conditions of insulated and stirred, loading nano silvery-titanium dioxide silicon sol solution 200g of preparation is slowly added to
Into above-mentioned emulsification system, feed time is controlled in 0.5h；Charging is pungent to mixed liquor addition coupling agent triethoxy after finishing
For base silane to 1wt%, insulated and stirred stops heating after reacting 2h, is down to room temperature, appropriate hexamethylene is added
Or phosphate, to 20mg/L, ammonium hydroxide adjusts pH about 7.2, is sealed；Up to the antibacterial barrier coat at film liquid.Obtained suppression
Colloidal particles particle size is 80-100nm in bacterium barrier coat liquid, storage-stable 30 weeks or so under air-proof condition.
Take it is above-mentioned at film liquid using PVC board as basal plane carry out surface dip-coating processing, be dried to obtain transparent film, film
Thick 0.18mm, elongation at break about 420%, adhesive force is excellent, and water resistance is excellent, and toughness is strong, easily removes, film light transmittance 87%.
Embodiment 2
Antibacterial barrier coat is prepared into film liquid
1) in the reaction unit equipped with stirring and heating condensation, by the surfactant allyloxy nonyl of concentration 30%
Phenoxypropanol polyoxyethylene ethereal solution is slowly added into 60 DEG C of deaeration resin mixture liquors of 1kg preparation, so that in mixed liquor
Surfactant final mass score is 2wt%；1h is quickly stirred after charging, is then emulsified using ultrasonic emulsification
System base fluid, ultrasonic power 200W, time 15min.
2) under the conditions of insulated and stirred, loading nano silvery-titanium dioxide silicon sol solution 350g of preparation is slowly added to
Into above-mentioned emulsification system, feed time is controlled in 0.5h；Charging is pungent to mixed liquor addition coupling agent triethoxy after finishing
For base silane to 1.5wt%, insulated and stirred stops heating after reacting 2h, is down to room temperature, and appropriate cosmocil stearate acid is added
To 30mg/L, ammonium hydroxide adjusts pH about 7.3, is sealed for salt or phosphate；Up to the antibacterial barrier coat at film liquid.It is obtained
Colloidal particles median size is 80-100nm in antibacterial barrier coat liquid, storage-stable 30 weeks under air-proof condition.
Comparative example 1
1) according to the same steps 1 of embodiment 1) prepare emulsification system.
2) under stirring condition, 0.02mmol nano-Ag particles are slowly added into above-mentioned emulsification system, insulated and stirred is anti-
Stop heating after answering 2h, be down to room temperature, ammonium hydroxide adjusts pH about 7.2, is sealed；Up to coating at film liquid.It is obtained it is antibacterial every
Viscosity is larger at from 25 DEG C of coating solution, and after 1 week is placed under air-proof condition, nano silver agglomeration occurs in microexamination discovery,
It can not store up long.
Effect example 1
Anti-microbial property test is carried out at film liquid prepares coating film with embodiment 1 and comparative example, selects Escherichia coli and gold
Staphylococcus aureus is experimental strain, and the specific test method is as follows.
1) glass substrate is placed in first and accordingly stands 0.5 minute in film liquid, film is lifted with the speed of 2-3mm/s,
It is cooling after wet film drying is dry, it repeats membrane 2 times.
2) the strain solution even of certain diluted concentration is applied on a series of diaphragms, uses power at room temperature
For the ultraviolet lamp irradiation diaphragm 30min of 25W, light source is 80-100cm away from height of specimen.It is subsequently placed in constant temperature in plating medium
37 DEG C of culture 36h, detect the colony count of its remaining bacteria.Wherein, to exclude interference of the ultraviolet light to experimental result, to wait bacterium
Liquid is coated in plating medium through the same terms ultraviolet irradiation as the blank control in the case of no film；With the coating of equivalent bacterium solution
Culture is in plating medium to obtain clump count before ultraviolet processing.
In addition, parallel test group of the setting without ultraviolet irradiation is to investigate the film sterilizing rate under non-illuminated conditions, group
Classification setting is tested with ultraviolet lighting.
The calculating of bacteriostasis rate is calculated as follows:
Bacteriostasis rate=(1- (clump count before clump count/ultraviolet processing after ultraviolet processing)) × 100%.
As a result it see the table below 1-2 (result round numerical value).
1 film of table is to Escherichia coli anti-microbial property
2 film of table is to Staphylococcus aureus anti-microbial property
As can be seen from the table, in ultraviolet lighting group and non-light group, the antibacterial ability of embodiment film is thinner than comparative example
Film strong antibacterial, and without film test group only pass through it is ultraviolet antibacterial.By taking Escherichia coli as an example, ultraviolet light bacteriostasis rate is only
27%, this illustrates that the antibacterial ability of film is leading position.For the interference for further excluding ultraviolet light, the non-light group knot of setting
Fruit also indicates that, even if embodiment film still has very high antibacterial ability under non-illuminated conditions, antibiotic rate is up to 97%.Root
According to comparative example as a result, due to comparative example at film liquid be free of titanium dioxide, even across ultraviolet light assist, bacteriostasis rate still compared with
It is low, when this explanation is without titanium dioxide film need auxiliary UV illumination could obtain 90% bactericidal effect, and embodiment group
After the silica solution component of titania-doped-nano silver, film can have excellent antibacterial energy under non-illuminated conditions
Power, this illustrates that the nano silver in silica solution component is mesoporous two for antibacterial with important synergistic effect under non-illuminated conditions
The concertedness useful supplement of silica supported nano-sized silver constituent.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (9)
1. a kind of biocidal property barrier coat for medical inspection platform is at the preparation method of film liquid, described to contain solid at film liquid
Microparticle, comprising: loading nano silvery-titanium dioxide silica solution component, the organically-modified mesoporous silicon oxide of doping nano-Ag
Antibacterial composite microsphere component, compound organic resin component, hexamethylene or phosphate and other auxiliary agent groups
Point, which is characterized in that preparation step is as follows:
S1: preparation is containing nano silver-titanium dioxide silica sol liquid；
S2: organically-modified mesoporous silicon oxide-nanometer silver antimicrobial complex microsphere is prepared；
S3: antibacterial complex microsphere-polyvinyl alcohol dispersion liquid is prepared using the antibacterial complex microsphere in step S2；
S4: compound organic resin coats the antibacterial microballoon；
S5: resin emulsification system base fluid is prepared；
S6: the mixing of emulsification system base fluid and silica sol liquid compound, addition cosmocil stearate, thus obtain it is described it is antibacterial every
From coating at film liquid.
2. preparation method as described in claim 1, which is characterized in that detailed process is as follows by step S1:
(1) under the conditions of being protected from light, stabilizer is added into silver nitrate solution, stirs, reducing agent sodium borohydride solution, side is then added dropwise
Side stirring is added dropwise, after completion of dropwise addition, continues magnetic agitation 2-6h, obtains clear and bright Nano silver solution；
(2) appropriate above-mentioned Nano silver solution is taken, is slowly added dropwise into the 5-10% silica sol liquid of 10-20 times of volume, is protected from light condition
Lower ultrasonic disperse is uniform；
(3) under the conditions of 30-35 DEG C of bath temperature and magnetic agitation, a certain amount of nano-titanium dioxide is added and continues to be protected from light stirring
2-6 hours, obtain loading nano silvery-titanium dioxide silica solution.
3. preparation method as claimed in claim 2, which is characterized in that the silver nitrate solution concentration is 1-2mM；The boron hydrogen
Change sodium solution is 5mM-20mM.
4. preparation method as described in claim 1, which is characterized in that step S2 is specific as follows:
(1) it prepares organically-modified mesoporous silicon dioxide micro-sphere: taking meso-porous titanium dioxide Si powder and appropriate organic modifiers, respectively
It is scattered in distilled water, two kinds of dispersion solution is heated to 60 DEG C and are mixed, DMF solvent is added and silane coupling agent stirs
After mixing 1-3h, vacuum pump is filtered, and filter cake is cleaned with deionized water, and drying and grinding obtains organically-modified silicon dioxide microsphere；
Wherein, the organic modifiers are selected from polyvinylpyrrolidone；
(2) in the reaction unit equipped with stirring and thermometer, by the improved silica aqueous microsphere dispersion liquid of 10-100mg/ml
With appropriate AgNO3Solution mixing is protected from light stirring 1-5h at room temperature, the sodium borohydride solution of proportional quantities is then added dropwise, in 0-10
DEG C continue to stir 1-3h, after reaction, the complex microsphere dispersion liquid of preparation is centrifuged, discards supernatant liquid, solid is distributed to water
In, obtain organically-modified mesoporous silicon oxide-nanometer silver antimicrobial complex microsphere, repeated centrifugation, the process of dispersion 1-2 times with pure
Change antibacterial complex microsphere.
5. preparation method as described in claim 1, which is characterized in that step S3 is specific as follows:
At 60-65 DEG C, resulting antibacterial complex microsphere is added in the polyvinyl alcohol clear solution of 1-5wt%, magnetic force stirs
30-60min is mixed, then ultrasonic vibration dispersion 10-15min, magnetic agitation 30-60min is micro- to get antibacterial again after ultrasonic vibration
Grain dispersion liquid；Wherein, the mass percent of antibacterial microballoon is 10-20% in antibacterial complex microsphere dispersion liquid.
6. preparation method as described in claim 1, which is characterized in that step S4 is specific as follows:
(1) PVDF particle is added in DMF solvent, it is 20- that 1-3h is stirred under 60 DEG C of waters bath with thermostatic control and obtains mass percent
30% PVDF solution；By mass fraction be 15-20% polyacrylate acetone soln and above-mentioned PVDF solution in mass ratio
1:0.5-1 mixing, it is 0.5-1% that pore-foaming agent to mass fraction, which is added, is stirred evenly up to compound organic resin solution；
(2) low whipping speed is 200-500rpm and under conditions of temperature is 50 DEG C~60 DEG C, by above-mentioned antibacterial complex microsphere point
Dispersion liquid is in being slowly added into compound resin solution, then low whipping speed is 300-500rpm and temperature is to stir at 50 DEG C~60 DEG C
Mix mixing 2-6h；Ultrasonic vibration 15-20min removes bubble；Wherein, antibacterial complex microsphere dispersion liquid and compound resin solution quality
Amount ratio is 1:1-5.
7. preparation method as described in claim 1, which is characterized in that step S5-S6 is specific as follows:
(1) in the reaction unit equipped with stirring and condensation, polymerisable surfactant solution is slowly added into 50-55 DEG C
In deaeration resin mixture liquor, the mass fraction that polymerisable surfactant is added in control is 1-3wt%；Ultrasound after stirring 0.5-1h
Wave emulsifies to obtain emulsification system, ultrasonic power 200-500W, time 10-20min；
(2) under the conditions of insulated and stirred, the silicon sol solution of above-mentioned loading nano silvery-titanium dioxide is slowly added into above-mentioned emulsification
In system, feed time is controlled in 0.5h；It feeds and silane coupling agent is added to 0.5-2wt%, heat preservation to mixed liquor after finishing
Be stirred to react after 1-2h and stop heating, be down to room temperature, appropriate hexamethylene or phosphate is added, adjust pH to
7-7.6 is to get the antibacterial barrier coat at film liquid；
Preferably, hexamethylene or phosphate is added to 10-50mg/L；Emulsification system and silicon sol solution
Mass ratio is 1:0.1-0.5.
8. the antibacterial barrier coat that -7 preparation methods are prepared according to claim 1 is at film liquid or film.
9. antibacterial barrier coat described in claim 8 is at film liquid or film for medical inspection operating platform surface coated treatment
Purposes.
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