CN103160786A - Nano coating preparation method and antibiosis nano coating prepared by nano coating - Google Patents
Nano coating preparation method and antibiosis nano coating prepared by nano coating Download PDFInfo
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Abstract
The invention reveals a preparation method of a nano coating, which employs plasma discharge for pretreating a substrate, an organic monomer with polymerization capability is introduced in a plasma cavity in a gas form to generate the organic monomer plasma, the polymerization is generated in the plasma cavity to generate the polymer plasma, and polymer plasma is deposited on the substrate surface to form the polymerization deposition of the nano coating. The invention also comprises an antibiosis nano layer prepared by the method of the invention. The nano coating and a substrate material can be combined with firm covalent bond to realize non-pharmacological antibiosis; compared with a traditional antibiosis coating, the antibiosis nano coating has the advantages of low cost and safe usage; the method of the invention can keep most characteristic groups of the organic monomer, and is in favor of design of antibiosis efficacy of the nano coating; and the antibiosis nano coating can keep killing or opposing a plurality of bacteria and mould in a long time, and the antibiosis effect is good, and the antimicrobial spectrum is wide.
Description
Technical field
The present invention relates to a kind of preparation method of nano coating and by the antimicrobial nano coating that the method prepares, relate in particular to a kind of method and a kind of antimicrobial nano coating that is applicable to medicine and hygiene fields that adopts the low temperature plasma polymerization technology to prepare nano coating.
Background technology
Along with the raising of medical level and health of people consciousness, self have killing or suppress microbial function a class new function anti-biotic material and use its antimicrobial coating technology to be used for more and more the fields such as medical field, household supplies, household electrical appliance, food product pack.Common antimicrobial coating mainly contains three major types by materials classification on the market:
the first kind is metallic compound antiseptic-germicide coating, mainly to utilize silver, copper, the antibacterial ability of the metals such as zinc so antimicrobial coating, wherein silver ions coating antibiotic and sterilizing effect is best, the most commonly used, Chinese patent CN101125970A, CN101073434A and CN102026589A, and US Patent No. 4340043, US6087549 etc. disclose the technology for preparing coating with the silver-ion antibiotic material, but the general cost of this metal compound coating is higher, if and might cause heavy metal poisoning in human body for medium-term and long-term medical inserting, and cause the body fluid salt deposit,
Equations of The Second Kind is the organic antibacterial agent coating, comprise the polymkeric substance antiseptic-germicide coating that organic molecule antiseptic-germicide coating and conventional chemical polymerization obtain, organic molecule coating such as Chinese patent CN101545203, CN101418517, the disclosed quaternary ammonium salt of US5064613 and US8092824 and derivatives class antiseptic-germicide coating thereof, polymkeric substance antiseptic-germicide coating such as Chinese patent CN1292806C, CN100346847C, the disclosed chitosans such as CN100413546 and US Patent No. 7597903 and US6936345, the natural polymer antiseptic-germicide coatings such as dextran, such organic antibacterial agent coating antibiotic spectrum substantially is better, cost is also far below the silver ions coating, but still exist obvious defective: 1. organic molecule antiseptic-germicide coating is more unstable, easily cause its organic micromolecule compound to decompose and discharge, thereby reduction anti-microbial property, be difficult to satisfy medium-term and long-term antibiotic, and whether the product of its decomposition difficult to calculate or release produces harm to human body, 2. polymkeric substance antiseptic-germicide coating is comparatively stable, but because it is generally with spraying, dip-coating, plated film, the technique such as electroless plating or collosol and gel makes, make between this type coating and base material bonding force a little less than, in use easily produce the phenomenon of coating stripping,
The 3rd class is microbiotic or medication coat, as microbiotic or medication coats such as Chinese patent CN100346847C, CN101653635 and the disclosed penicillin of US Patent No. 5217493, Tubulicid, Ciprofloxacin, Minocycline HCl, Rifampins, this type coating is mostly by making bacterium death or inactivation with the mutual special biological action of bacterium, relatively be suitable for acute or short-term sterilization fast antibiotic, easily induce the generation drug-resistant bacteria if it is used as long-term antibiotic medium.Therefore, develop a kind of good anti-bacterial effect, persistence is strong, comparatively stable and with low cost again simultaneously, and the less antimicrobial coating of the side effect that human body is produced is imperative.
Low-temperature plasma is material the 4th attitude after solid-state, liquid, gaseous state, produces the mixture that comprises electronics, various ion, atom and free radical by impressed voltage.Existing plasmaassisted processing is used to make the novel material of extraordinary premium properties, develops new chemical substance and chemical process, and processing, transformation and refining material and surface thereof are as thin film deposition, plasma polymerization, plasma spraying etc.
the existing technology for preparing plasma polymer coating or film at medical implant or rack surface, as patent U.S. US20110060402A1 and the disclosed technology of US20050249777A1, or as document " L. Zhou, et al., Thin Solid Films, 2012,520 (7): 2505-2509 ", " T. He, et al., 2012, Materials Science and Engineering C, 32:1025 – 1031 ", " Wang Haibo etc., functional materials, 2008,39 (7): 1193-1196 ", " Yang Zhilu etc., functional materials, 2008,39 (9): 1559-1566 ", " Yan Feng etc., biomedical engineering research, 2008,27 (4): 268-271 " disclosed technology is mainly first with ethylene glycol, vinylformic acid, methacrylic acid, the monomers such as hexamethyldisiloxane become polymeric coating or film in the substrate material surface polycondensation, then come biomacromolecule by this coating or film, as protein, antibody, enzyme, nucleic acid etc. produce fixing, absorption or repulsive interaction, thus complete medical implant or rack surface hydrophilic, anticoagulation, physiologically acceptable, the improvement of the performance such as anticorrosive, or directly add medicine to carry out in vivo further pharmacological agent in polymeric coating or film.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of nano coating and the antimicrobial nano coating that is prepared by the method, relate in particular to a kind of low temperature plasma polymerization technology that adopts and the multiclass organic monomer is aggregated to the preparation method of multiple substrate material surface, and a kind of antimicrobial nano coating that is applicable to medicine and hygiene fields.Purpose of the present invention realizes by following technical proposals:
A kind of preparation method of nano coating comprises the steps:
Pre-treatment step: will put into plasma chamber by the substrate that base material is made indoor, described plasma chamber is vacuumized, and pass into non-polymerization gas, and open described plasma chamber electrode supply and discharge, pre-treatment is carried out in described substrate;
Aggregation deposition step: will have the organic monomer of polymerizing power to pass into described plasma chamber with gas form indoor, opening described plasma chamber electrode supply discharges, produce the organic monomer plasma body, described organic monomer plasma body is at the indoor polymerization reaction take place of described plasma chamber, generation polymkeric substance plasma body, and described polymkeric substance is plasma-deposited forms nano coating at described substrate surface.
The inventive method preferably, the discharge mode of the plasma chamber electrode supply in described pre-treatment step or described aggregation deposition step is continuous radio frequency discharge, its continuous radio frequency discharge power is 10 W～1000 W.
The inventive method preferably, the discharge mode of the plasma chamber electrode supply in described pre-treatment step or described aggregation deposition step is pulsed rf discharge, its pulsed rf discharge power is that 10 W～1000 W, pulse duty factor are 1 ﹪～99 ﹪.
The inventive method preferably, the indoor vacuum keep of plasma chamber in described pre-treatment step is between 5 Pa～100 Pa, temperature remains on below 45 ℃, and the flow of described non-polymerization gas is between 10 sccm～100 sccm, and be 2 min～20 min described discharge time.
The inventive method preferably, the indoor vacuum keep of plasma chamber in described aggregation deposition step is between 5 Pa～100 Pa, temperature remains on below 45 ℃, and between 20 sccm～200 sccm, be 10 min～120 min described discharge time to described organic monomer with the flow of gas.
The inventive method preferably, described non-polymerization gas is one or more combinations that comprise argon gas, helium or nitrogen.
The inventive method preferably, described organic monomer is for containing at least following one or more combinations of a kind of special groups: oxyethane, ethylene glycol, polyoxyethylene glycol, glycol dimethyl ether, vinylcarbinol, halogenated phenols, propenal, vinylformic acid, allylamine, n-Butyl Amine 99, acrylamide, vinyl cyanide, methacrylonitrile, ethyleneimine, amino acid, amino acid derivative, pyridine, pyridine derivate, guanidine, guanidine derivative, quaternary ammonium salt, quaternary ammonium salt derivative, season phosphonium salt and derivative thereof.
The inventive method preferably, described special groups comprise epoxy group(ing), alcoholic extract hydroxyl group, phenolic hydroxyl group, aldehyde radical, carboxyl, itrile group, primary amine groups, secondary amine, tertiary amine groups, quaternary amine base, imido grpup, acid halide group or season phosphino-.
The inventive method preferably, the base material of making described substrate material layer comprises following at least a natural macromolecular material: Mierocrystalline cellulose, chitosan, collagen protein, fibroin, poly(lactic acid) or poly lactic-co-glycolic acid.
The inventive method preferably, the base material of making described substrate material layer comprises following at least a synthesized polymer material: polypropylene, high density polyethylene(HDPE), acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polymethylmethacrylate, polyvinyl chloride, tetrafluoroethylene, polymeric amide, urethane, silicon rubber or latex.
The inventive method preferably, the base material of making described substrate material layer comprises following at least a material: silicon chip, glass, stainless steel, nickelalloy, titanium alloy.
The inventive method preferably, described substrate is fiber, silk thread, woven cloths, non-woven fabrics, film, thin slice, conduit or the support of being made by base material.
The present invention also comprises a kind of antimicrobial nano coating, and described antimicrobial nano coating is the nano coating that the preparation method by above-mentioned any one nano coating makes.
A kind of antimicrobial nano coating of the present invention further, the thickness of described nano coating is 20 nm～200 nm.
Application of the present invention is implemented its remarkable technique effect is mainly reflected in:
1. the nano coating of the polymkeric substance plasma body of the inventive method preparation and base material are by covalent bonds very firmly, are difficult for being destroyed by extraneous bad border or affecting, thereby realize that non-medication is antibiotic;
2. compare with these a few class antimicrobial coatings of conventional silver ion, organic molecule, conventional polymer and antibiotic medicine, the present invention has the advantages that cost is lower, use safety;
The nano coating of the plasma polymer that 3. prepares by the inventive method can keep most of characteristic groups of organic monomer, is conducive to the design of nano coating antibiotic effect;
4. the nano coating of the inventive method preparation can keep killing or resisting the effect of various bacteria and mould in a long time, and good anti-bacterial effect and antimicrobial spectrum are wider.
Following constipation closes accompanying drawing, the specific embodiment of the present invention is described in further detail, so that technical solution of the present invention is easier to understand, grasp.
Description of drawings
Figure 1A is the microscope 2D figure figure of the embodiment of the present invention 1 ethyleneimine-vinylformic acid plasma body binary copolymerization antimicrobial nano coating;
Figure 1B is the microscope 3D figure figure of the embodiment of the present invention 1 ethyleneimine-vinylformic acid plasma body binary copolymerization antimicrobial nano coating;
Fig. 2 is the x-ray photoelectron energy spectrogram of the embodiment of the present invention 1 ethyleneimine-vinylformic acid plasma body binary copolymerization antimicrobial nano coating;
Fig. 3 is the x-ray photoelectron energy spectrogram of the embodiment of the present invention 2 ethyleneimines-vinylformic acid plasma body binary copolymerization antimicrobial nano coating;
Fig. 4 A is no dyeing on the embodiment of the present invention 1 ethyleneimine-vinylformic acid plasma body binary copolymerization antimicrobial nano coating, bacterial adhesion schematic diagram in its surface;
After Fig. 4 B is the embodiment of the present invention 1 ethyleneimine-vinylformic acid plasma body binary copolymerization antimicrobial nano coating EB dyeing, bacterial adhesion schematic diagram in its surface under UV-light;
After Fig. 4 C is the embodiment of the present invention 1 ethyleneimine-vinylformic acid plasma body binary copolymerization antimicrobial nano coating AO dyeing, bacterial adhesion schematic diagram in its surface under UV-light.
Embodiment
The present invention will be described below in conjunction with accompanying drawing and specific embodiment, for embodiment product of the present invention or method are made the generality illustration, help to understand better the present invention, but can't limit the scope of the invention.Experimental technique described in following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
the present invention is intended to provide a kind of method of utilizing the low temperature plasma polymerization technology to prepare nano coating, and corresponding at least a polymkeric substance antimicrobial nano coating with it, can obtain the coating of different antibiotic effects by the technique of selecting different organic monomers and/or regulation and control plasma polymerization, and, can prepare by the organic monomer plasma body group and the polymkeric substance that conventional polymerization technique can not get or is difficult to obtain, and make the polymerisate Direct precipitation in reaction process on base material and form firm covalent bonding, make the coating of deposition have good resistance to chemical reagents, thermostability and mechanical property.The preparation method of a kind of nano coating of the present invention comprises the steps:
Pre-treatment step: will put into plasma chamber by the substrate that base material is made indoor, described plasma chamber is vacuumized, and pass into non-polymerization gas, and open described plasma chamber electrode supply and discharge, pre-treatment is carried out in described substrate.
Aggregation deposition step: will have the organic monomer of polymerizing power to pass into described plasma chamber with gas form indoor, opening described plasma chamber electrode supply discharges, produce the organic monomer plasma body, described organic monomer plasma body is at the indoor polymerization reaction take place of described plasma chamber, generation polymkeric substance plasma body, and described polymkeric substance is plasma-deposited forms nano coating at described substrate surface.Reaction product forms stable, nano coating that have certain anti-microbial activity on specific base material, and finally realizes antibacterial applications together with base material.
The concrete ground of implementing, the discharge mode of the plasma chamber electrode supply in described pre-treatment step or described aggregation deposition step is continuous radio frequency discharge, its continuous radio frequency discharge power is 10 W～1000 W.The discharge mode of the plasma chamber electrode supply in described pre-treatment step or described aggregation deposition step is pulsed rf discharge, and its pulsed rf discharge power is that 10 W～1000 W, pulse duty factor are 1 ﹪～99 ﹪.The indoor vacuum keep of plasma chamber in described pre-treatment step is between 5 Pa～100 Pa, and temperature remains on below 45 ℃, and the flow of described non-polymerization gas is between 10 sccm～100 sccm, and be 2 min～20 min described discharge time.The indoor vacuum keep of plasma chamber in described aggregation deposition step is between 5 Pa～100 Pa, temperature remains on below 45 ℃, between 20 sccm～200 sccm, be 10 min～120 min described discharge time to described organic monomer with the flow of gas.
The described non-polymerization gas of the embodiment of the present invention is one or more combinations that include but not limited to argon gas, helium or nitrogen; Described organic monomer is for containing at least following one or more combinations of a kind of special groups: oxyethane, ethylene glycol, polyoxyethylene glycol, glycol dimethyl ether, vinylcarbinol, halogenated phenols, propenal, vinylformic acid, allylamine, n-Butyl Amine 99, acrylamide, vinyl cyanide, methacrylonitrile, ethyleneimine, amino acid, amino acid derivative, pyridine, pyridine derivate, guanidine, guanidine derivative, quaternary ammonium salt, quaternary ammonium salt derivative, season phosphonium salt and derivative thereof.Under the plasma polymerization condition, above-mentioned group with anti-microbial activity, be former organic monomer with special groups or/and the new group that polyreaction generates, nano coating surface in new moulding exists with higher density and/or higher stability, makes this nano coating directly bacterium and the mould of kill harmful.Above-mentioned organic monomer suitably changes combination in described scope and the coating that makes has anti-microbial activity in various degree.As, carry out polyquaternium coating and the simple plasma polymer coating for preparing take halogenated phenols as monomer of the generation of plasma body binary copolymerization as monomer take vinyl pyridine and halogenated phenols, the former generally has very strong anti-microbial activity, and latter's anti-microbial activity is relatively weak.
The described special groups of the embodiment of the present invention include but not limited to epoxy group(ing), alcoholic extract hydroxyl group, phenolic hydroxyl group, aldehyde radical, carboxyl, itrile group, primary amine groups, secondary amine, tertiary amine groups, quaternary amine base, imido grpup, acid halide group or season phosphino-.Further, the base material of making described substrate material layer comprises following at least a natural macromolecular material: Mierocrystalline cellulose, chitosan, collagen protein, fibroin, poly(lactic acid) or poly lactic-co-glycolic acid; The base material of making described substrate material layer comprises following at least a synthesized polymer material: polypropylene, high density polyethylene(HDPE), acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polymethylmethacrylate, polyvinyl chloride, tetrafluoroethylene, polymeric amide, urethane, silicon rubber or latex; The base material of making described substrate material layer comprises following at least a material: silicon chip, glass, stainless steel, nickelalloy, titanium alloy; Described substrate is fiber, silk thread, woven cloths, non-woven fabrics, film, thin slice, conduit or the support of being made by base material.
Can prepare a kind of antimicrobial nano coating according to the inventive method, the thickness of described nano coating is 20 nm～200 nm.
By covalent bonds very firmly by the nano coating of the polymkeric substance plasma body of the inventive method preparation and base material, can or not be difficult under normal circumstances discharge or dissociate from base material, and final realization is that non-medication is antibiotic, can form alternative to these a few class antimicrobial coatings of silver ions, organic molecule, conventional polymer and antibiotic medicine.Also occur using the antimicrobial product of the similar technology manufacturing of the present invention on domestic market, so the technology that the present invention comprises is in medical treatment and the quite wide application prospect of health field.
［ embodiment 1 ］The preparation of the ethyleneimine take silicon chip as substrate material layer-vinylformic acid plasma body copolymer antimicrobial nano coating
Take smooth silicon chip as base material, carry out the plasma body copolymerization with ethyleneimine and two kinds of organic monomers of vinylformic acid.At first, take argon gas as non-polymerization gas, silicon chip is carried out pre-treatment, argon flow amount is 10 sccm, keeps vacuum tightness ~ 60 Pa discharge 3 min in continuous radio-frequency plasma, and discharge power is 80 W; With the vaporization and with certain mixed in molar ratio in the subsidiary grafting instrument of plasma body instrument respectively of two kinds of organic monomers, as 8:2, or 9:1; Opening grafting instrument valve introduces the gas of mix monomer in plasma chamber with the flow of 60 sccm, at vacuum tightness 70 Pa, discharge power is that under the condition of 80 W, discharge 15 min make ethyleneimine-vinylformic acid plasma body copolymer antimicrobial nano coating.
［ embodiment 2 ］The preparation of the ethyleneimine take cellulosic nonwoven fabric as substrate material layer-vinylformic acid plasma body binary copolymerization antimicrobial nano coating
Select with embodiment 1 in identical ethyleneimine and vinylformic acid mix monomer carry out the plasma body copolymerization, substrate material layer is cellulosic nonwoven fabric.At first, take nitrogen as non-polymerization gas, cellulosic nonwoven fabric is carried out pre-treatment, nitrogen flow is 30 sccm, keeps vacuum tightness ~ 40 Pa 2 min that discharge in pulsed radiofrequency plasma, and pulse duty factor is 40%, and discharge power is 50 W; The mol ratio of mix monomer is different from embodiment 1, as 6:4, or 7:3, monomer mixed gas after gasification is introduced in plasma chamber with the flow of 80 sccm, keep discharge 20 min under vacuum tightness 50 Pa, discharge power 50 W conditions, make ethyleneimine-vinylformic acid plasma body copolymer antimicrobial nano coating.
［ embodiment 3 ］Ethylene glycol-propenal take medical stainless steel as substrate-acrylic acid plasma body terpolymer antimicrobial nano coating
Take the medical stainless steel sheet as substrate, select ethylene glycol, propenal and three kinds of monomers of vinylformic acid to carry out the plasma body copolymerization, with embodiment 1, they are all vaporizations and with certain mixed in molar ratio in the subsidiary grafting instrument of separately plasma body instrument also, as 6:2:2, or 7:1.5:1.5.At first, the medical stainless steel sheet is put into plasma chamber pre-treatment under argon gas atmosphere, argon flow amount is 10 sccm, keeps vacuum tightness 70 Pa discharge 2 min in continuous radio-frequency plasma, and discharge power is 100 W; The gas of mix monomer is introduced in plasma chamber with the flow of 60 sccm, kept condition discharge 10 min of vacuum tightness 70 Pa, discharge power is 150 W.With acetal, hemiacetal or/and the Plasma Copolymer coating of their hydration unit tightly is combined in stainless steel surface, because the hydration unit of acetal, hemiacetal and they all has stronger spectrum germ resistance, and give especially its quite high stability under the preparation condition of plasma body, almost do not have irritating aldehydes to discharge, can effectively ensure medical safe.
［ embodiment 4 ］Vinylformic acid pentachloro-phenolic ester take latex catheter as substrate-4-vinylpyridine) plasma body binary copolymerization antimicrobial nano coating
Take latex catheter as base material, select a kind of vinylpyridine monomers and a kind of halogenated phenols monomer to carry out the plasma body copolymerization, as vinylformic acid pentachloro-phenolic ester and 4-vinylpridine, they can enter plasma chamber and with certain mixed in molar ratio by spraying plant separately, as 1:1, or 10:1.At first, with latex catheter pre-treatment under nitrogen atmosphere, argon flow amount is 20 sccm, vacuum tightness 80 Pa, and discharge 5 min in the plasma chamber of continuous radio frequency, discharge power is 200 W; The spraying of mix monomer is introduced in plasma chamber with the flow (equivalent flow) of 100 sccm, kept condition discharge 45 min of vacuum tightness 80 Pa, discharge power is also 200 W.Existence due to halo phenolic group and tertiary amine groups, plasma polymerization can generate stable QAS polymer (for isotactic multipolymer, segmented copolymer and graft copolymer three's mixture), the QAS polymer coating has very strong sterilizing ability and stability, and harmless.
The antimicrobial nano coating of above each embodiment, thickness all below 100 nm, affect the mechanical property of base material hardly, and can relatively be evenly distributed in substrate material surface.For example, as shown in Figure 1A, Figure 1B and table 1, the ethyleneimine in embodiment 1-vinylformic acid plasma body binary copolymerization antimicrobial nano coating dense distribution is at silicon chip surface, the coating heaving and dipping is little, thickness is about 50 nm, and r.m.s. roughness only has 2.9 nm, and the surface is smoother still.Above all coatings preparation technology preferably are not limited to the described Parameter Conditions of each embodiment.
The roughness of ethyleneimine in table 1 embodiment 1-vinylformic acid plasma body binary copolymerization antimicrobial nano coating
| R.m.s. roughness Rq | Arithmetic average roughness Ra | Maximal roughness Rmax | | |
| Embodiment | ||||
| 1 | 2.9 | 2.2 | 46.2 | 46.2 |
Table 2 is to test according to the x-ray photoelectron power spectrum of the antimicrobial nano coatingsurface in embodiment 1 and embodiment 2 the element molar content analysis that obtains, result shows: although the antimicrobial nano coating in embodiment 1 and 2 is all by two kinds of identical monomer polymerizations, but because technique and monomer ratio are different, be coated with formable layer after elemental composition not identical yet; In two kinds of antimicrobial nano coatings, the N/C ratio is far above the blank sample of not doing separately any coating processing, N element and C, O become principal element together, this is because contain amine in the monomer of participation plasma polymerization, and other elements, photoelectron signal as the Si element becomes very faint, and this is obviously the coated cause of covering of most of original surface.As shown in Figures 2 and 3, the stronger characteristic peaks such as N 1s, C 1s and O 1s can be used to do element bonding scheme quantitative analysis further, and result shows that the N element major part in coating is primary amine and secondary amine, and has a large amount of carboxyls.Therefore, can keep most of characteristic groups of monomer by the plasma polymer coating of the above method preparation, this extremely is conducive to the design of nano coating antibiotic effect.
Elemental composition analysis corresponding to nano coating surface in table 2 embodiment 1 and embodiment 2
Fig. 4 A, Fig. 4 B and Fig. 4 C are the antibacterial experiments of ethyleneimine in embodiment 1-vinylformic acid plasma body binary copolymerization antimicrobial nano coating, and this experiment is 10 with, concentration resuspended through the PBS damping fluid
7The streptococcus aureus bacteria suspension of cfu/ml drops in the silicon chip surface for preparing the binary copolymerization coating, silicon chip carrier is cultivated 2 h in the incubator of 37 ° of C, rinses silicon chip surface with PBS after cultivate finishing, then fluorochromine and at the fluorescence microscopy Microscopic observation.Result shows: in 2 h, there is a large amount of streptococcus aureuses to adhere on ethyleneimine-vinylformic acid plasma body binary copolymerization coating, but can find out according to character and the coloration result of EB and AO dyestuff, see Table 3, the bacterium major part that adheres in 2 h all is killed, only having minority is existing state, and 2 h antibacterial effects are very obvious.The antimicrobial nano coating for preparing by the technology of the present invention can keep killing or resisting the effect of various bacteria and mould in a long time, and is not limited to bacterial classification and time of mentioning in above method.
The character of table 3 EB fuel and AO dyestuff
The above is only the preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (14)
1. the preparation method of a nano coating, is characterized in that comprising the steps:
Pre-treatment step: will put into plasma chamber by the substrate that base material is made indoor, described plasma chamber is vacuumized, and pass into non-polymerization gas, and open described plasma chamber electrode supply and discharge, pre-treatment is carried out in described substrate;
Aggregation deposition step: will have the organic monomer of polymerizing power to pass into described plasma chamber with gas form indoor, opening described plasma chamber electrode supply discharges, produce the organic monomer plasma body, described organic monomer plasma body is at the indoor polymerization reaction take place of described plasma chamber, generation polymkeric substance plasma body, and described polymkeric substance is plasma-deposited forms nano coating at described substrate surface.
2. the preparation method of a kind of nano coating according to claim 1, it is characterized in that: the discharge mode of the plasma chamber electrode supply in described pre-treatment step or described aggregation deposition step is continuous radio frequency discharge, and its continuous radio frequency discharge power is 10 W～1000 W.
3. the preparation method of a kind of nano coating according to claim 1, it is characterized in that: the discharge mode of the plasma chamber electrode supply in described pre-treatment step or described aggregation deposition step is pulsed rf discharge, and its pulsed rf discharge power is that 10 W～1000 W, pulse duty factor are 1 ﹪～99 ﹪.
4. the preparation method of a kind of nano coating according to claim 1, it is characterized in that: the indoor vacuum keep of the plasma chamber in described pre-treatment step is between 5 Pa～100 Pa, temperature remains on below 45 ℃, the flow of described non-polymerization gas is between 10 sccm～100 sccm, and be 2 min～20 min described discharge time.
5. the preparation method of a kind of nano coating according to claim 1, it is characterized in that: the indoor vacuum keep of plasma chamber in described aggregation deposition step is between 5 Pa～100 Pa, temperature remains on below 45 ℃, between 20 sccm～200 sccm, be 10 min～120 min described discharge time to described organic monomer with the flow of gas.
6. the preparation method of a kind of nano coating according to claim 1, it is characterized in that: described non-polymerization gas is one or more combinations that comprise argon gas, helium or nitrogen.
7. the preparation method of a kind of nano coating according to claim 1 is characterized in that: described organic monomer is for containing at least following one or more combinations of a kind of special groups: oxyethane, ethylene glycol, polyoxyethylene glycol, glycol dimethyl ether, vinylcarbinol, halogenated phenols, propenal, vinylformic acid, allylamine, n-Butyl Amine 99, acrylamide, vinyl cyanide, methacrylonitrile, ethyleneimine, amino acid, amino acid derivative, pyridine, pyridine derivate, guanidine, guanidine derivative, quaternary ammonium salt, quaternary ammonium salt derivative, season phosphonium salt and derivative thereof.
8. the preparation method of a kind of nano coating according to claim 7 is characterized in that: described special groups comprise epoxy group(ing), alcoholic extract hydroxyl group, phenolic hydroxyl group, aldehyde radical, carboxyl, itrile group, primary amine groups, secondary amine, tertiary amine groups, quaternary amine base, imido grpup, acid halide group or season phosphino-.
9. the preparation method of a kind of nano coating according to claim 1, it is characterized in that: the base material of making described substrate material layer comprises following at least a natural macromolecular material: Mierocrystalline cellulose, chitosan, collagen protein, fibroin, poly(lactic acid) or poly lactic-co-glycolic acid.
10. the preparation method of a kind of nano coating according to claim 1, it is characterized in that: the base material of making described substrate material layer comprises following at least a synthesized polymer material: polypropylene, high density polyethylene(HDPE), acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polymethylmethacrylate, polyvinyl chloride, tetrafluoroethylene, polymeric amide, urethane, silicon rubber or latex.
11. the preparation method of a kind of nano coating according to claim 1 is characterized in that: the base material of making described substrate material layer comprises following at least a material: silicon chip, glass, stainless steel, nickelalloy, titanium alloy.
12. the preparation method of a kind of nano coating according to claim 1 is characterized in that: described substrate is fiber, silk thread, woven cloths, non-woven fabrics, film, thin slice, conduit or the support of being made by base material.
13. an antimicrobial nano coating comprises the nano coating that the preparation method by described any one nano coating of claim 1 to 12 makes.
14. a kind of antimicrobial nano coating according to claim 13 is characterized in that: the thickness of described nano coating is 20 nm～200 nm.
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| CN103768700A (en) * | 2013-07-03 | 2014-05-07 | 苏州睿研纳米医学科技有限公司 | Protein antimicrobial catheter and manufacturing method thereof |
| CN104788707A (en) * | 2015-04-22 | 2015-07-22 | 广州洁特生物过滤股份有限公司 | Preparation method of super-hydrophilic cell growth surface |
| CN106731225A (en) * | 2016-12-07 | 2017-05-31 | 盐城工学院 | A kind of antibacterial filtrate and its method for sorting |
| WO2018214446A1 (en) * | 2017-05-21 | 2018-11-29 | 江苏菲沃泰纳米科技有限公司 | Method for preparing multi-functional protective nano coating by means of low-power continuous discharge |
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