CN101623763B - Method for synthesizing nano silver by taking macromolecules as template on surface of film - Google Patents

Abstract

The invention provides a method for synthesizing nano silver by taking macromolecules as a template on the surface of a film, belonging to the field of nano silver synthesization. The method uses a medium to resist a discharge device and takes ammonia or allylamine as a discharge monomer and uses argon as an auxiliary gas and grafts amidogens on the surfaces of a PET film, a BOPP film and a PE film under a vacuum condition; methanol is dropped to the films with the surfaces grafted with the amidogens under an ice-bath condition, and then methyl acrylate is dropped to the films for reacting; a mixed solution of quadrol and the methanol is dropped to the films for reacting; the reaction is repeated to generate a polyamide branch-shaped macromolecule sample with the tail end provided with the amidogens from 1.0 G to 5.0 G; and after the reaction is completed, the polyamide branch-shaped macromolecule sample is cleanly washed and placed into a silver nitrate solution for stirring, and then taken out and placed into a sodium borohydride solution for stirring so as to be synthesized into the nano silver after being washed. The invention widens the application of the films, such as the application in sterilization packaging, and enables the films to have the characteristics of precious metal nano particles. The films prepared by the invention can be widely applied to the industries, i.e. superconduction, chemical engineering, optics, electron, electrical appliance, and the like.

Description

At film surface is the method for template synthesizing nano-silver with big molecule

Technical field:

The present invention relates to a kind of new method of synthesizing nano-silver, especially at the film surface synthesizing nano-silver.

Background technology:

Nano Silver is a kind of emerging functional material, be widely used in industries such as biology, superconduction, chemical industry, optics, electronics, electrical equipment, have broad application prospects, nano particle forms film on base material, is nanometer technology is turned to practical application by experiment a important step.Silver/polymer composites has had the good characteristic of Nano Silver and polymer simultaneously, and gives material some special or new functions, thereby it is had broad application prospects at numerous areas such as photonic propulsion, electronics, biomedicine and information material.Therefore its preparation has become the hot subject that present nano materials research field is paid close attention to application.Nano silver particles is filled into the silver/polymer nanocomposites that forms in the polymer, can shows the performances such as magnetic, light, sound, heat, electricity and superconduction that the conventional polymer material does not have, very big using value is arranged in each field.

In recent ten years, the physical method and the chemical method of multiple preparation nano silver particles have been developed.Explore low-cost, easy, efficient and have the nano silver particles preparation method of industrial prospect, be the emphasis of this area research always.Physical method has high energy mechanical ball-milling method, luminescence method, using vaporization condensation process etc.The physical method principle is simple, its shortcoming be to instrument and equipment have relatively high expectations, the producing cost costliness, be applicable to that mainly the size and dimension to nano silver particles requires not high industrialization preparation.The synthetic nano silver particles of chemical method is mainly used in fields such as the higher optics of nano particle performance requirement, electricity and biomedicines, and its key technology is how to control the size of particle, narrower size distribution and obtain specific and uniform crystalline structure.Chemical preparation process mainly contains liquid phase chemical reduction method, electrochemical reducing, photoreduction method etc.In addition, the structure and properties of the self assembly of nano silver particles and orderly assembling film also gets more and more people's extensive concerning in recent years, the research that very little nano silver particles or the semiconductor nano silver particles of particularly particle diameter being distributed is assembled into orderly superlattices and photoelectric properties thereof has evoked people's very big interest especially, for people provide possibility by the size of control nano particle or the photoelectric properties of interparticle distance research solid composite membrane.

The preparation method of silver/polymer nanocomposites mainly contains in-situ method, interfacial polymerization and hole method etc.Exist substantial connection between the technology of preparing of argentum nano composite material and its structure and the performance.Hole method wherein is at first polymer to be made porous material, and the hole can form " hole " at polymer surfaces, also can run through polymer network and forms " tunnel ".Then with the nano silver particles landfill for preparing in " hole " or be embedded in " tunnel " lining.Zhang etc. [1] have developed a kind of novel method for preparing Nano Silver/polystyrene compound particle, promptly use 1,2-dichloroethylene etching and swelling polystyrene colloid surface produce the hole at colloid surface, then silver particles evenly are coated on the position of respective hole.In the method, silver particles is directly synthetic in the core of colloidal particle surface voids, has not only avoided the generation of surperficial energy, and can improve the ability that hole core and nucleus combine.The concentration of 1,2-dichloroethene is the key of covered effect.The thickness of clad and roughness can be controlled effectively the crystallizable one-tenth ordered structure of prepared composite by changing the formaldehyde consumption in the nucleus growth process.This method for coating is easy and general, also coats other metallics applicable to polystyrene colloid.Kim etc. [2] utilize hole method nano silver particles in homogeneous precipitation on the porous surface of polyethylene glycol dimethyl ester and acrylonitrile copolymer equally.X-ray diffraction is the result show, formed strong absorption between the CN key on silver and polymer microballoon surface, thereby the tiny nano silver particles with cubic can be embedded in the copolymer micropore equably.But the method for document [1] is polystyrene surface etching and swelling to have been destroyed the structure of polymer with solvent, application to film has certain restriction, the method of document [2] is to utilize the hole of polymer surfaces to precipitate the filling nano silver particles, the method is more limited can only to be used for cuniculate polymer, not too suitable to general film surface.

[1]Zhang?J?H，Liu?H?Y，Wang?ZL，et?al.Materials?Letters，2007，61：4579-4582

[2]KimJ?W，Lee?J?E，Kim?S?J，et?al.Polymer，2004，45：4741-4747

Summary of the invention

The object of the invention: be to solve at the film surface synthesizing nano-silver, it is more extensive to make film use, be applied to sterilization packaging, and make film have some characteristics of noble metal nano particles, be widely used in industries such as superconduction, chemical industry, optics, electronics, electrical equipment.

In PET, BOPP, PE film surface grafted amine groups, serves as that nuclear by chemical reaction, at film surface synthetic convergence type polyamide-amide (PAMAM) with this amido with the DBD discharge.Be raw material again with the silver nitrate, sodium borohydride is a reducing agent, and convergence type polyamide-amide (PAMAM) dendrimer is the template stabilizing agent of holding concurrently, synthesizing nano-silver particle in macromolecular hole, and prove that by experiment restraining and sterilizing bacteria is respond well.

The invention provides a kind of is the method for template synthesizing nano-silver at film surface with big molecule, it is characterized in that, may further comprise the steps:

Using the dielectric barrier discharge device, under vacuum condition, is discharge monomer with ammonia or allylamine, is assist gas with the argon gas, in PET (PET), BOPP (bidirectional stretching polypropylene film) or PE (polyethylene) film surface grafted amine groups,

Using the dielectric barrier discharge device, under vacuum condition, is discharge monomer with ammonia or allylamine, is assist gas with the argon gas, at PET, bidirectional stretching polypropylene film or polyethylene film surface grafting amido;

Wherein supply frequency is 45-60KHZ, and discharging gap is 1-4mm, NH ₃Flow is 300-400ml/min, and the allylamine flow is 100-400mL/min, and the Ar flow is 1-4L/min, and be 30s-6min discharge time;

Film slitting behind the surface grafting amido is become small pieces, put into container, drip methyl alcohol under the condition of ice bath, splash into methyl acrylate again, in the dark under 20-35 degree centigrade of water bath condition, magnetic stirring reaction 22-30 hour; Liquid in the container is poured out, and dripping ethylenediamine is 1 with the methanol quality ratio: 2-1: 4 mixed solution, and in the dark under 20-35 degree centigrade of water bath condition, magnetic stirring reaction 22-30 hour; The end that repeats above-mentioned reaction generation 1.0G-5.0G is the daiamid dendritic macromole sample of amido;

It is clean with washed with methanol to react the sample that finishes, and puts into liquor argenti nitratis ophthalmicus and stirs, and puts into sodium borohydride solution after take out the back and stirs, and has promptly synthesized Nano Silver after the cleaning.Mixing time got final product more than general half an hour in this step, and examples of implementation are unified for being half an hour to contrast for each embodiment effect all has unified standard.

Effect of the present invention: 1, the using plasma charging method is at organic film (PET, BOPP, PE) surface grafting amido;

2,, serve as that to utilize Michael addition and amidation process to synthesize end be the PAMAM dendritic macromole of amido to nuclear with the amido of film surface at film surface comprehensive utilization plasma treatment and chemical reduction method;

3, be that the substrate synthesizing nano-silver has good restraining and sterilizing bacteria with film (PET, BOPP, PE), make film be applied to the packing of food better, and make film have the characteristics such as some magnetic, superconduction, light, sound, heat and electricity of noble metal nano particles, be widely used in industries such as superconduction, chemical industry, optics, electronics, electrical equipment.

The specific embodiment:

Example 1: it is to be under the 30Pa condition at the vacuum background that dielectric barrier discharge (DBD) plasma technique discharge ammonia is handled the sample experiment, with the ammonia is reaction monomers, with Ar is assist gas, place quartz glass plate and sample P ET film at DBD device bottom crown, comes polymerization amido functional group.Supply frequency is 50KHZ, and discharging gap is 2mm, NH ₃Flow is 400ml/min, and the Ar flow is 3L/min, and be 40s discharge time.

The PET film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 25 degrees centigrade of water bath condition, magnetic stirring reaction 24 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 15g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 25 degrees centigrade of water bath condition magnetic stirring reaction 24 hours with black plastic paper.1. and 2. once generate the PAMAM of 2.0G reaction repeated.

2.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l the liquor argenti nitratis ophthalmicus beaker in, and stir half an hour with magnetic, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.2mol/l over to, after diaphragm taken out put into deionized water and clean, can obtain the pet sheet face synthetic be the Nano Silver of template with 2.0GPAMAM.

The clip diameter is the blank PET film of 8mm, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PET base Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 16h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 0.29mm.

The clip diameter is the blank PET film of 8mm respectively, and above-mentioned silver nitrate concentration is 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PET base Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 16h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 049,0.22,0.19mm.

Example 2: the experiment of dielectric barrier discharge (DBD) plasma technique discharge ammonia treatments B OPP film is to be under the 30Pa condition at the vacuum background, with the ammonia is reaction monomers, with Ar is assist gas, place quartz glass plate and sample BOPP film at DBD device bottom crown, come polymerization amido functional group.Supply frequency is 55KHZ, and discharging gap is 2mm, NH ₃Flow is 300ml/min, and the Ar flow is 3L/min, and be 40s discharge time.

The BOPP film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 20 degrees centigrade of water bath condition, magnetic stirring reaction 28 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 15g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 20 degrees centigrade of water bath condition magnetic stirring reaction 28 hours with black plastic paper.1. and 2. once generate the PAMAM of 2.0G reaction repeated.

2.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l the liquor argenti nitratis ophthalmicus beaker in, and stir half an hour with magnetic, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.3mol/l over to, after diaphragm taken out put into deionized water and clean, can obtain the BOPP film surface synthetic be the Nano Silver of template with 2.0GPAMAM.

The clip diameter is a 8mmBOPP film film, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place BOPP thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 0.31mm.

The clip diameter is a 8mmBOPP film film, and above-mentioned silver nitrate concentration is respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place BOPP thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 0.54,0.28,0.20mm.

Example 3: it is to be under the 30Pa condition at the vacuum background that dielectric barrier discharge (DBD) plasma technique discharge ammonia is handled the experiment of PE film, with the ammonia is reaction monomers, with Ar is assist gas, place quartz glass plate and sample P E film at DBD device bottom crown, comes polymerization amido functional group.Supply frequency is 56KHZ, and discharging gap is 2mm, NH ₃Flow is 400ml/min, and the Ar flow is 4L/min, and be 60s discharge time.

The PE film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 25 degrees centigrade of water bath condition, magnetic stirring reaction 26 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 10g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 25 degrees centigrade of water bath condition magnetic stirring reaction 26 hours with black plastic paper.1. and 2. once generate the PAMAM of 2.0G reaction repeated.

2.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l the liquor argenti nitratis ophthalmicus beaker in, and stir half an hour with magnetic, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.26mol/l over to, after diaphragm taken out put into deionized water and clean, can obtain the PE film surface synthetic be the Nano Silver of template with 2.0GPAMAM.

The clip diameter is the 8mmPE film, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 16h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 0.33mm.

The clip diameter is the 8mmPE film, and above-mentioned silver nitrate concentration is respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 16h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 0.48,0.29,0.21mm.

Example 4: it is to be under the 20Pa condition at the vacuum background that dielectric barrier discharge (DBD) plasma technique discharge allylamine is handled the experiment of PET film, with the allylamine is reaction monomers, with Ar is assist gas, place quartz glass plate and sample P ET film at DBD device bottom crown, come polymerization amido functional group.Supply frequency is 50KHZ, and discharging gap is 4mm, and the allylamine flow is 100ml/min, and the Ar flow is 1L/min, and be 4min discharge time.

The PET film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 30 degrees centigrade of water bath condition, magnetic stirring reaction 22 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 10g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 30 degrees centigrade of water bath condition magnetic stirring reaction 22 hours with black plastic paper.1. and 2. once generate the PAMAM of 2.0G reaction repeated.

2.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l the liquor argenti nitratis ophthalmicus beaker in, and stir half an hour with magnetic, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.4mol/l over to, after diaphragm taken out put into deionized water and clean, can obtain the pet sheet face synthetic be the Nano Silver of template with 2.0GPAMAM.

The clip diameter is the blank PET film of 8mm, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PET base Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 16h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 0.32mm.

The clip diameter is the blank PET film of 8mm, and above-mentioned silver nitrate concentration is respectively 0.1mol/l, 0.001mol/l, and the Nano Silver diaphragm that 0.0001mol/l synthesizes is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PET base Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 16h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 0.45,0.28,0.21mm.

Example 5: the experiment of dielectric barrier discharge (DBD) plasma technique discharge allylamine treatments B OPP film is to be under the 20Pa condition at the vacuum background, with the allylamine is reaction monomers, with Ar is assist gas, place quartz glass plate and sample BOPP film at DBD device bottom crown, come polymerization amido functional group.Supply frequency is 55KHZ, and discharging gap is 3mm, and the allylamine flow is 100ml/min, and the Ar flow is 1L/min, and be 6min discharge time.

The BOPP film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 25 degrees centigrade of water bath condition, magnetic stirring reaction 24 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.Drip the mixed solution of 4g ethylenediamine and 16g methyl alcohol under the condition of ice bath, there-necked flask is encased in the dark under 25 degrees centigrade of water bath condition magnetic stirring reaction 24 hours with black plastic paper.1. and 2. once generate the PAMAM of 2.0G reaction repeated.

2.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l the liquor argenti nitratis ophthalmicus beaker in, and stir half an hour with magnetic, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.3mol/l over to, after diaphragm taken out put into deionized water and clean, can obtain the BOPP film surface synthetic be the Nano Silver of template with 2.0GPAMAM.

The clip diameter be 8mmBOPP film film, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place BOPP thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 0.35mm.

The clip diameter is that 8mmBOPP film film, above-mentioned silver nitrate concentration are respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place BOPP thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 0.50,0.31,0.28mm.

Example 6: it is to be under the 20Pa condition at the vacuum background that dielectric barrier discharge (DBD) plasma technique discharge allylamine is handled the experiment of PE film, with the allylamine is reaction monomers, with Ar is assist gas, place quartz glass plate and sample allylamine film at DBD device bottom crown, come polymerization amido functional group.Supply frequency is 50KHZ, and discharging gap is 2mm, and the allylamine flow is 200ml/min, and the Ar flow is 2L/min, and be 6min discharge time.

The PE film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 30 degrees centigrade of water bath condition, magnetic stirring reaction 26 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 15g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 25 degrees centigrade of water bath condition magnetic stirring reaction 26 hours with black plastic paper.1. and 2. once generate the PAMAM of 2.0G reaction repeated.

2.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l the liquor argenti nitratis ophthalmicus beaker in, and stir half an hour with magnetic, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.25mol/l over to, after diaphragm taken out put into deionized water and clean, can obtain the PE film surface synthetic be the Nano Silver of template with 2.0GPAMAM.

The clip diameter be 8mmPE film, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 18h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 0.36mm.

The clip diameter is that 8mmPE film, above-mentioned silver nitrate concentration are respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 18h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 0.56,0.31,0.23mm.

Example 7: it is to be under the 30Pa condition at the vacuum background that dielectric barrier discharge (DBD) plasma technique discharge ammonia is handled the sample experiment, with the ammonia is reaction monomers, with Ar is assist gas, place quartz glass plate and sample P ET film at DBD device bottom crown, comes polymerization amido functional group.Supply frequency is 45KHZ, and discharging gap is 1mm, NH ₃Flow is 400ml/min, and the Ar flow is 3L/min, and be 60s discharge time.

The PET film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 25 degrees centigrade of water bath condition, magnetic stirring reaction 24 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.Drip the mixed solution of 4g ethylenediamine and 12g methyl alcohol under the condition of ice bath, there-necked flask is encased in the dark under 25 degrees centigrade of water bath condition magnetic stirring reaction 24 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 3.0G for twice.

3.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.25mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the pet sheet face synthetic be the Nano Silver of template with 3.0GPAMAM.

The clip diameter is the blank PET film of 8mm, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PET base Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 18h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 0.46mm.

Cut-off directly is the blank PET film of 8mm, and above-mentioned silver nitrate concentration is respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PET base Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 18h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 0.61,0.39,0.30mm.

Example 8: the experiment of dielectric barrier discharge (DBD) plasma technique discharge ammonia treatments B OPP film is to be under the 30Pa condition at the vacuum background, with the ammonia is reaction monomers, with Ar is assist gas, place quartz glass plate and sample BOPP film at DBD device bottom crown, come polymerization amido functional group.Supply frequency is 55KHZ, and discharging gap is 2mm, NH ₃Flow is 300ml/min, and the Ar flow is 3L/min, and be 40s discharge time.

The BOPP film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 35 degrees centigrade of water bath condition, magnetic stirring reaction 22 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 20g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 35 degrees centigrade of water bath condition magnetic stirring reaction 22 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 3.0G for twice.

3.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.25mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the BOPP film surface synthetic be the Nano Silver of template with 3.0GPAMAM.

The clip diameter is a 8mmBOPP film film, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place BOPP thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 0.48mm.

The clip diameter is a 8mmBOPP film film, and above-mentioned silver nitrate concentration is respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place BOPP thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 0.62,0.38,0.30mm.

Example 9: it is to be under the 30Pa condition at the vacuum background that dielectric barrier discharge (DBD) plasma technique discharge ammonia is handled the experiment of PE film, with the ammonia is reaction monomers, with Ar is assist gas, place quartz glass plate and sample P E film at DBD device bottom crown, comes polymerization amido functional group.Supply frequency is 56KHZ, and discharging gap is 2mm, NH ₃Flow is 400ml/min, and the Ar flow is 4L/min, and be 40s discharge time.

The PE film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 20 degrees centigrade of water bath condition, magnetic stirring reaction 30 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 20g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 30 degrees centigrade of water bath condition magnetic stirring reaction 28 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 3.0G for twice.

3.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.26mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the PE film surface synthetic be the Nano Silver of template with 3.0GPAMAM.

The clip diameter is the 8mmPE film, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 0.54mm.

The clip diameter is the 8mmPE film, and above-mentioned silver nitrate concentration is respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 0.79,0.43,0.36mm.

Example 10: it is to be under the 20Pa condition at the vacuum background that dielectric barrier discharge (DBD) plasma technique discharge allylamine is handled the experiment of PET film, with the allylamine is reaction monomers, with Ar is assist gas, place quartz glass plate and sample P ET film at DBD device bottom crown, come polymerization amido functional group.Supply frequency is 54KHZ, and discharging gap is 4mm, and the allylamine flow is 100ml/min, and the Ar flow is 1L/min, and be 4min discharge time.

The PET film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 25 degrees centigrade of water bath condition, magnetic stirring reaction 24 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 10g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 25 degrees centigrade of water bath condition magnetic stirring reaction 24 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 3.0G for twice.

3.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.2mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the pet sheet face synthetic be the Nano Silver of template with 3.0GPAMAM.

The clip diameter is the blank PET film of 8mm, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PET base Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 16h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 0.52mm.

The clip diameter is the blank PET film of 8mm, and above-mentioned silver nitrate concentration is respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PET base Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 16h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 0.61,0.46,0.34mm.

Example 11: the experiment of dielectric barrier discharge (DBD) plasma technique discharge allylamine treatments B OPP film is to be under the 20Pa condition at the vacuum background, with the allylamine is reaction monomers, with Ar is assist gas, place quartz glass plate and sample BOPP film at DBD device bottom crown, come polymerization amido functional group.Supply frequency is 58KHZ, and discharging gap is 2mm, and the allylamine flow is 100ml/min, and the Ar flow is 1L/min, and be 5min discharge time.

The BOPP film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 25 degrees centigrade of water bath condition, magnetic stirring reaction 28 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 15g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 25 degrees centigrade of water bath condition magnetic stirring reaction 28 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 3.0G for twice.

3.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.2mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the BOPP film surface synthetic be the Nano Silver of template with 3.0GPAMAM.

The clip diameter be 8mmBOPP film film, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place BOPP thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 18h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 0.50mm.

The clip diameter is that 8mmBOPP film film, above-mentioned silver nitrate concentration are respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place BOPP thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 18h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 0.58,0.40,0.31mm.

Example 12: it is to be under the 20Pa condition at the vacuum background that dielectric barrier discharge (DBD) plasma technique discharge allylamine is handled the experiment of PE film, with the allylamine is reaction monomers, with Ar is assist gas, place quartz glass plate and sample allylamine film at DBD device bottom crown, come polymerization amido functional group.Supply frequency is 60KHZ, and discharging gap is 2mm, and the allylamine flow is 200ml/min, and the Ar flow is 2L/min, and be 3min discharge time.

The PE film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 25 degrees centigrade of water bath condition, magnetic stirring reaction 24 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 20g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 25 degrees centigrade of water bath condition magnetic stirring reaction 24 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 3.0G for twice.

3.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.2mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the PE film surface synthetic be the Nano Silver of template with 3.0GPAMAM.

The clip diameter be 8mmPE film, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 18h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 0.56mm.

The clip diameter is that 8mmPE film, above-mentioned silver nitrate concentration are respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 18h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 0.67,0.43,0.32mm.

Example 13: it is to be under the 30Pa condition at the vacuum background that dielectric barrier discharge (DBD) plasma technique discharge ammonia is handled the sample experiment, with the ammonia is reaction monomers, with Ar is assist gas, place quartz glass plate and sample P ET film at DBD device bottom crown, comes polymerization amido functional group.Supply frequency is 58KHZ, and discharging gap is 3mm, NH ₃Flow is 400ml/min, and the Ar flow is 3L/min, and be 50s discharge time.

The PET film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 30 degrees centigrade of water bath condition, magnetic stirring reaction 24 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 15g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 30 degrees centigrade of water bath condition magnetic stirring reaction 24 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 4.0G for three times.

4.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.35mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the pet sheet face synthetic be the Nano Silver of template with 4.0GPAMAM.

The clip diameter is the blank PET film of 8mm, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PET base Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 0.86mm.

The clip diameter is that 8mmPET film, above-mentioned silver nitrate concentration are respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 0.98,0.73,0.59mm.

Example 14: the experiment of dielectric barrier discharge (DBD) plasma technique discharge ammonia treatments B OPP film is to be under the 30Pa condition at the vacuum background, with the ammonia is reaction monomers, with Ar is assist gas, place quartz glass plate and sample BOPP film at DBD device bottom crown, come polymerization amido functional group.Supply frequency is 56KHZ, and discharging gap is 2mm, NH ₃Flow is 300ml/min, and the Ar flow is 3L/min, and be 30s discharge time.

The BOPP film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 20 degrees centigrade of water bath condition, magnetic stirring reaction 30 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 15g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 20 degrees centigrade of water bath condition magnetic stirring reaction 30 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 4.0G for three times.

4.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.42mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the BOPP film surface synthetic be the Nano Silver of template with 4.0GPAMAM.

The clip diameter is a 8mmBOPP film film, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place BOPP thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 16h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 0.96mm.

The clip diameter is a 8mmBOPP film film, and above-mentioned silver nitrate concentration is respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place BOPP thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 16h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 1.24,0.88,0.72mm.

Example 15: it is to be under the 30Pa condition at the vacuum background that dielectric barrier discharge (DBD) plasma technique discharge ammonia is handled the experiment of PE film, with the ammonia is reaction monomers, with Ar is assist gas, place quartz glass plate and sample P E film at DBD device bottom crown, comes polymerization amido functional group.Supply frequency is 48KHZ, and discharging gap is 1mm, NH ₃Flow is 400ml/min, and the Ar flow is 4L/min, and be 40s discharge time.

The PE film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 25 degrees centigrade of water bath condition, magnetic stirring reaction 24 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 20g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 25 degrees centigrade of water bath condition magnetic stirring reaction 24 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 4.0G for three times.

4.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l beaker in, and stir half an hour with magnetic, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.3mol/l over to, after diaphragm taken out put into deionized water and clean, can obtain the PE film surface synthetic be the Nano Silver of template with 4.0GPAMAM.

The clip diameter is the 8mmPE film, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 18h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 0.98mm.

The clip diameter is the 8mmPE film, and above-mentioned silver nitrate concentration is respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 18h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 1.12,0.86,0.74mm.

Example 16: it is to be under the 20Pa condition at the vacuum background that dielectric barrier discharge (DBD) plasma technique discharge allylamine is handled the experiment of PET film, with the allylamine is reaction monomers, with Ar is assist gas, place quartz glass plate and sample P ET film at DBD device bottom crown, come polymerization amido functional group.Supply frequency is 50KHZ, and discharging gap is 3mm, and the allylamine flow is 100ml/min, and the Ar flow is 1L/min, and be 4min discharge time.

The PET film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 30 degrees centigrade of water bath condition, magnetic stirring reaction 24 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 15g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 30 degrees centigrade of water bath condition magnetic stirring reaction 24 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 4.0G for three times.

4.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.4mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the pet sheet face synthetic be the Nano Silver of template with 4.0GPAMAM.

The clip diameter is the blank PET film of 8mm, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PET base Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 1.02mm.

The clip diameter is the blank PET film of 8mm, and above-mentioned silver nitrate concentration is respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PET base Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 1.31,0.94,0.82mm.

Example 17: the experiment of dielectric barrier discharge (DBD) plasma technique discharge allylamine treatments B OPP film is to be under the 20Pa condition at the vacuum background, with the allylamine is reaction monomers, with Ar is assist gas, place quartz glass plate and sample BOPP film at DBD device bottom crown, come polymerization amido functional group.Supply frequency is 60KHZ, and discharging gap is 2mm, and the allylamine flow is 100ml/min, and the Ar flow is 1L/min, and be 5min discharge time.

The BOPP film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 25 degrees centigrade of water bath condition, magnetic stirring reaction 24 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 15g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 25 degrees centigrade of water bath condition magnetic stirring reaction 24 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 4.0G for three times.

4.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.26mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the BOPP film surface synthetic be the Nano Silver of template with 4.0GPAMAM.

The clip diameter be 8mmBOPP film film, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place BOPP thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 18h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 0.98mm.

The clip diameter is that 8mmBOPP film film, above-mentioned silver nitrate concentration are respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place BOPP thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 18h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 1.21,0.84,0.75mm.

Example 18: it is to be under the 20Pa condition at the vacuum background that dielectric barrier discharge (DBD) plasma technique discharge allylamine is handled the experiment of PE film, with the allylamine is reaction monomers, with Ar is assist gas, place quartz glass plate and sample allylamine film at DBD device bottom crown, come polymerization amido functional group.Supply frequency is 50KHZ, and discharging gap is 2mm, and the allylamine flow is 200ml/min, and the Ar flow is 2L/min, and be 6min discharge time.

The PE film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 35 degrees centigrade of water bath condition, magnetic stirring reaction 22 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 10g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 35 degrees centigrade of water bath condition magnetic stirring reaction 22 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 4.0G for three times.

4.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.3mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the PE film surface synthetic be the Nano Silver of template with 4.0GPAMAM.

The clip diameter be 8mmPE film, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 16h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 1.06mm.

The clip diameter is that 8mmPE film, above-mentioned silver nitrate concentration are respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 16h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 1.32,0.96,0.79mm.

Example 19: it is to be under the 30Pa condition at the vacuum background that dielectric barrier discharge (DBD) plasma technique discharge ammonia is handled the sample experiment, with the ammonia is reaction monomers, with Ar is assist gas, place quartz glass plate and sample P ET film at DBD device bottom crown, comes polymerization amido functional group.Supply frequency is 56KHZ, and discharging gap is 2mm, NH ₃Flow is 400ml/min, and the Ar flow is 3L/min, and be 50s discharge time.

The PET film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 25 degrees centigrade of water bath condition, magnetic stirring reaction 24 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 20g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 25 degrees centigrade of water bath condition magnetic stirring reaction 24 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 5.0G for four times.

5.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.4mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the pet sheet face synthetic be the Nano Silver of template with 5.0GPAMAM.

The clip diameter is the blank PET film of 8mm, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PET base Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 1.24mm.

The clip diameter is the blank PET film of 8mm, and above-mentioned silver nitrate concentration is respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PET base Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 1.45,1.09,0.89mm.

Example 20: the experiment of dielectric barrier discharge (DBD) plasma technique discharge ammonia treatments B OPP film is to be under the 30Pa condition at the vacuum background, with the ammonia is reaction monomers, with Ar is assist gas, place quartz glass plate and sample BOPP film at DBD device bottom crown, come polymerization amido functional group.Supply frequency is 58KHZ, and discharging gap is 2mm, NH ₃Flow is 300ml/min, and the Ar flow is 3L/min, and be 30s discharge time.

The BOPP film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 30 degrees centigrade of water bath condition, magnetic stirring reaction 24 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 15g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 30 degrees centigrade of water bath condition magnetic stirring reaction 24 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 5.0G for four times.

5.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.26mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the BOPP film surface synthetic be the Nano Silver of template with 5.0GPAMAM.

The clip diameter is a 8mmBOPP film film, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place BOPP thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 18h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 1.20mm.

The clip diameter is a 8mmBOPP film film, and above-mentioned silver nitrate concentration is respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place BOPP thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 18h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 1.46,1.01,0.89mm.

Example 21: it is to be under the 30Pa condition at the vacuum background that dielectric barrier discharge (DBD) plasma technique discharge ammonia is handled the experiment of PE film, with the ammonia is reaction monomers, with Ar is assist gas, place quartz glass plate and sample P E film at DBD device bottom crown, comes polymerization amido functional group.Supply frequency is 56KHZ, and discharging gap is 2mm, NH ₃Flow is 400ml/min, and the Ar flow is 4L/min, and be 40s discharge time.

The PE film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 25 degrees centigrade of water bath condition, magnetic stirring reaction 24 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 10g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 25 degrees centigrade of water bath condition magnetic stirring reaction 24 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 5.0G for four times.

5.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.35mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the PE film surface synthetic be the Nano Silver of template with 5.0GPAMAM.

The clip diameter is the 8mmPE film, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 1.26mm.

The clip diameter is the 8mmPE film, and above-mentioned silver nitrate concentration is respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 1.54,1.08,0.98mm.

Example 22: it is to be under the 20Pa condition at the vacuum background that dielectric barrier discharge (DBD) plasma technique discharge allylamine is handled the experiment of PET film, with the allylamine is reaction monomers, with Ar is assist gas, place quartz glass plate and sample P ET film at DBD device bottom crown, come polymerization amido functional group.Supply frequency is 50KHZ, and discharging gap is 3mm, and the allylamine flow is 100ml/min, and the Ar flow is 1L/min, and be 4min discharge time.

The PET film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 35 degrees centigrade of water bath condition, magnetic stirring reaction 22 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 15g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 35 degrees centigrade of water bath condition magnetic stirring reaction 22 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 5.0G for four times.

5.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.38mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the pet sheet face synthetic be the Nano Silver of template with 5.0GPAMAM.

The clip diameter is the blank PET film of 8mm, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PET base Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 16h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 1.22mm.

The clip diameter is the blank PET film of 8mm, and above-mentioned silver nitrate concentration is respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PET base Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 16h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 1.44,1.08,0.89mm.

Example 23: the experiment of dielectric barrier discharge (DBD) plasma technique discharge allylamine treatments B OPP film is to be under the 20Pa condition at the vacuum background, with the allylamine is reaction monomers, with Ar is assist gas, place quartz glass plate and sample BOPP film at DBD device bottom crown, come polymerization amido functional group.Supply frequency is 55KHZ, and discharging gap is 2mm, and the allylamine flow is 100ml/min, and the Ar flow is 1L/min, and be 6min discharge time.

The BOPP film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 20 degrees centigrade of water bath condition, magnetic stirring reaction 28 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.The mixed solution of Dropwise 5 g ethylenediamine and 15g methyl alcohol under the condition of ice bath encases there-necked flask in the dark under 20 degrees centigrade of water bath condition magnetic stirring reaction 28 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 5.0G for four times.

5.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.2mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the BOPP film surface synthetic be the Nano Silver of template with 5.0GPAMAM.

The clip diameter be 8mmBOPP film film, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place BOPP thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 18h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 1.28mm.

The clip diameter is that 8mmBOPP film film, above-mentioned silver nitrate concentration are respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place BOPP thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 18h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 1.59,1.09,0.98mm.

Example 24: it is to be under the 20Pa condition at the vacuum background that dielectric barrier discharge (DBD) plasma technique discharge allylamine is handled the experiment of PE film, with the allylamine is reaction monomers, with Ar is assist gas, place quartz glass plate and sample allylamine film at DBD device bottom crown, come polymerization amido functional group.Supply frequency is 50KHZ, and discharging gap is 2mm, and the allylamine flow is 200ml/min, and the Ar flow is 2L/min, and be 4min discharge time.

The PE film of the intact amido of grafting is cut into the small pieces of 1.25cm*2.5cm, put into the there-necked flask that magneton is housed, 1. drip 12g methyl alcohol under the condition of ice bath, splash into the 4g methyl acrylate again, with black plastic paper there-necked flask is encased, in the dark under 25 degrees centigrade of water bath condition, magnetic stirring reaction 24 hours.Generate the big molecule of 1.0G daiamid (PAMAM).2. the liquid in the there-necked flask is poured out, added methanol solution reaction product is cleaned, magnetic stirring and washing half an hour.Drip the mixed solution of 4g ethylenediamine and 12g methyl alcohol under the condition of ice bath, there-necked flask is encased in the dark under 25 degrees centigrade of water bath condition magnetic stirring reaction 24 hours with black plastic paper.1. and 2. reaction repeated generates the PAMAM of 5.0G for four times.

5.0GPAMAM is taken out ethylenediamine and the methyl acrylate that falls remained on surface with washed with methanol, put into respectively that 50ml concentration is housed is 0.1mol/l, 0.01mol/l, 0.001mol/l, 0.0001mol/l in the beaker of liquor argenti nitratis ophthalmicus, and stir half an hour, change immediately then that magnetic stirs half an hour in the sodium borohydride solution of 0.4mol/l over to magnetic, after diaphragm taken out put into deionized water and clean, can obtain the PE film surface synthetic be the Nano Silver of template with 5.0GPAMAM.

The clip diameter be 8mmPE film, above-mentioned silver nitrate concentration during for 0.01mol/l synthetic Nano Silver diaphragm respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is 1.28mm.

The clip diameter is that 8mmPE film, above-mentioned silver nitrate concentration are respectively 0.1mol/l, 0.001mol/l, and Nano Silver diaphragm synthetic during 0.0001mol/l is respectively as experimental group.Get the 0.5ml staphylococcus aureus and place 4.5ml physiological saline, use forced oscillation, bacterial classification is uniformly dispersed, stand-by bacteria suspension is made in dilution, and (bacteria suspension concentration is 10 ⁵About cfu/ml) annotate: cfu/mL refers to the microbiologic population's sum that contains in every ml sample.The bacteria suspension that makes is drawn 50 μ L inject culture dish, pour nutrient medium into, bacterium liquid and culture medium are mixed, build culture dish.Put super-clean bench air dry 5min.In the microbiological contamination flat board, place PE thin film based Nano Silver diaphragm for the test print, print and culture medium are combined closely.Build plate, put 37 ℃ of incubators, observed result behind the cultivation 17h with the diameter of the antibacterial ring of vernier caliper measurement, is represented with mm.Experiment draws blank film is not had fungistatic effect, and nanometer silverskin inhibition zone diameter is respectively 1.59,1.10,0.99mm.

Claims (1)

1. one kind is the method for template synthesizing nano-silver at film surface with big molecule, it is characterized in that, may further comprise the steps:

Using the dielectric barrier discharge device, under vacuum condition, is discharge monomer with ammonia or allylamine, is assist gas with the argon gas, at PET, bidirectional stretching polypropylene film or polyethylene film surface grafting amido;

Wherein supply frequency is 45-60KHZ, and discharging gap is 1-4mm, NH ₃Flow is 300-400ml/min, and the allylamine flow is 100-400mL/min, and the Ar flow is 1-4L/min, and be 30s-6min discharge time;

Film slitting behind the surface grafting amido is become small pieces, put into container, drip methyl alcohol under the condition of ice bath, splash into methyl acrylate again, in the dark under 20-35 degree centigrade of water bath condition, magnetic stirring reaction 22-30 hour; Liquid in the container is poured out, and dripping ethylenediamine is 1 with the methanol quality ratio: 2-1: 4 mixed solution, and in the dark under 20-35 degree centigrade of water bath condition, magnetic stirring reaction 22-30 hour; The end that repeats above-mentioned reaction generation 1.0G-5.0G is the polyamide-amide dendritic macromole sample of amido;

It is clean with washed with methanol to react the sample that finishes, and puts into liquor argenti nitratis ophthalmicus and stirs, and puts into sodium borohydride solution after the taking-up and stirs, and has promptly synthesized Nano Silver after the cleaning.