CN103242550B - Method for preparing anti-infectious medical material by plasma technology - Google Patents
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- CN103242550B CN103242550B CN201210027387.0A CN201210027387A CN103242550B CN 103242550 B CN103242550 B CN 103242550B CN 201210027387 A CN201210027387 A CN 201210027387A CN 103242550 B CN103242550 B CN 103242550B
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Abstract
The invention discloses a method for preparing an anti-infectious medical material by a plasma technology. The method comprises: in a vacuum condition, firstly, immersing a medical high-molecular material in argon plasma, then injecting nitrogen plasma and silver plasma on to a medical material surface, and finally obtaining the medical high-molecular material with surface anti- infectivity. The method is simple in operation, does not affect physical and chemical structures of material noumenon, and the high-molecular material after treated, has a stable surface structure, and has a long-acting and wide spectrum anti-infectious performance.
Description
Technical field
The present invention relates to modified polymer material, relate to particularly the method that adopts plasma technology to prepare medical use anti-infection macromolecular material.
Background technology
At present on the market or the various flexible materialss that use of hospital; comprise wound medical polymer film, burn medical polymer film etc.; they are commonly used to protect damaged tissue position to avoid extraneous injury again, create a good microenvironment, to promote the healing of wound to damaged tissue.If these materials do not possess anti-infective performance, tend to cause damaged tissue to infect or occur inflammatory phenomena, postpone or hinder healing or the regeneration of damaged tissue.For example, when burn protective membrane is polyethylene non-woven fabrics, the external world burning except its protection of needs in use procedure, not by infected by microbes, also needs it can kill or suppress the bacterium that wound has infected, and creates a good regeneration microenvironment to tissue of burn.
Current, the method of giving film antiseptic-germicide mainly concentrates on and in bulk material, adds the antiseptic-germicide such as silver, zinc, as steel and the manufacture method thereof of patent CN99800249.6 product having enhanced antibacterial action, it is by the appropriate silver that adds in stainless steel, there are in right amount one or more in silver particles, silver oxide and silver-colored sulfide on stainless surface, obtain germ resistance high and processibility and the good stainless steel plate of erosion resistance.If but use the method for film or non-woven fabrics, can increase preparation technology's difficulty of film or non-woven fabrics, cost is higher simultaneously.Report about material surface modifying aspect has, preparation method's (application number 200910308258.7) of the people's such as Tian Xiubo slow-release type skeleton-type Ti/Cu-Zn metal level antibacterial film adopts magnetron sputtering technique to deposit slow-release type skeleton-type TiN/Cu-Zn metal level at frosting, thereby give frosting anti-microbial property, the magnetron sputtering technique that this patent adopts forms coating on surface, this coating is often comparatively stable at block frosting, but often easily come off at soft film surface, this patent is not modified and is given material anti-microbial property the molecular structure of material simultaneously, mainly utilize zinc or copper to give antibacterial surface performance and only obtain its anti-microbial property by additional substance at outside surface, therefore, this technology is difficult to give flexible thin-film material lasting anti-microbial property.Liu Xuan bravely waits people's a kind of surface modifying method (application number 201110106021.8) of medical titanium metal material by the ion implantation medical titanium metal material of silver/nitrogen binary, this invention is by after nitrogen plasma Implanted Titanium metallic substance, generate titanium alloy, do not make material generate the nitrogenous organic chemistry group with anti-infective performance, inject nitrogen plasma is mainly in order to improve mechanical property and corrosion resistance nature simultaneously, anti-microbial property and the biocompatibility requirement that can comprise anti-infection property do not help, and anti-microbial property only derives from the injection of silver-colored plasma body.In addition, the people such as Liu Xianghuai, Wang Xi improves the method (publication number is: CN1385142A) of artificial cardiac valve material blood compatibility and safety in utilization, by ion implantation N+ heart valve leaflet surface of making to RESEARCH OF PYROCARBON, the method has only improved the blood compatibility of material, do not solve material surface anti-infective performance and and tissue between biocompatibility issues; The human hair such as Zhang Yiming, Chen Yu understands the surface modifying method (publication number is: CN101880402A) of medical grade silicon rubber, carbon ion is injected into silastic surface by the method, reach histocompatibility by improving its surface hydrophilicity, do not solve silastic surface infection problems; For another example, the people such as Zhao Jie, Liu Qianxiang has reported the method (publication number is: CN1827840) of preparing silver-enriched antibacterial film on medical RESEARCH OF PYROCARBON and TiN film, the method is only silver ions to be injected on RESEARCH OF PYROCARBON and TiN film and to reach antibacterial effect, RESEARCH OF PYROCARBON and TiN film belong to inorganic and metal_based material, the chemical structure on medical macromolecular materials surface is not modified in this invention, thereby improves its surface anti infection performance.
Therefore, a kind of technology need to be provided, the chemical structure that it can modify by generating the anti-infective chemical structures such as nitrogenous functional group medical macromolecular materials surface macromolecular chain, make macromolecular chain itself there is anti-infection ability, the silver-colored plasma body of collaborative injection, further to improve the anti-infective performance on medical molecular material surface, makes the anti-microbial property of macromolecular material more lasting simultaneously.
Summary of the invention
The technical problem to be solved in the present invention is to provide the method that adopts plasma technology to prepare medical use anti-infection macromolecular material; The method is cleaning material surface first medical macromolecular materials are immersed in to argon plasma under vacuum condition in, then nitrogen plasma is injected into medical macromolecular materials surface, finally obtains having surface anti infection medical macromolecular materials; Present method is simple to operate, does not affect the physical chemistry structure of material body, and the polymer surface Stability Analysis of Structures obtaining after processing has anti-infective performance long-acting, wide spectrum.
For solving the problems of the technologies described above, the invention provides the method that adopts plasma technology to prepare medical use anti-infection macromolecular material, comprise the following steps:
(1) be 1.0 × 10 at sealed vacuum degree
-2～1.0 × 10
-5under Pa condition, medical macromolecular materials are placed in to argon plasma 0.001～2 hour;
(2) nitrogen plasma is injected into medical macromolecular materials surface, reacts with macromolecular chain, generate nitrogenous functional group, obtain medical use anti-infection macromolecular material;
Wherein, described nitrogen plasma is N
2and/or NH
3there is the nitrogen plasma that plasma bodyization generates;
The implantation dosage of nitrogen plasma is 1.0 × 10
15～5.0 × 10
22ions/cm
2, injecting the degree of depth is 0.001～3 μ m.
In the present invention, the molecular structure generation chemical reaction of nitrogen plasma and macromolecular material, generate a large amount of nitrogenous organic groups at polymer surface, these nitrogenous organic groups have anti-infective performance, make macromolecular material have restraining effect to the Growth and reproduction of bacterium, also help the growth and breeding of cell and tissue simultaneously.
In actually operating, those skilled in the art can control the implantation dosage of nitrogen plasma and the injection degree of depth according to prior art.Due to the instrument difference using, each service data difference does not limit herein.
Conventionally, setting the argon flow amount passing into is 2SCCM～40SCCM.The effect of argon plasma is the generation that helps nitrogen plasma, and argon plasma constantly bombards macromolecular material simultaneously, makes macromolecular material have more C=C key to produce, and is more conducive to the generation of nitrogen-containing functional group.Final experimental result is had to promoter action to the flow of argon gas but impact is little, therefore argon flow amount do not limited.
Inject after nitrogen plasma at polymer surface, can obtain anti-infectious macromolecular material; But preferably,, described step (2) also comprises using silver as electrode, and silver-colored plasma body is injected to medical macromolecular materials surface; The implantation dosage of silver plasma body is 1.0 × 10
13～5.0 × 10
19ions/cm
2, injecting the degree of depth is 0.001～3 μ m.Injecting the silver-colored plasma body that reinjects outside nitrogen plasma, make the not only restraining effect of the Growth and reproduction to bacterium of medical material surface, even bacterium is had to killing action.
Conventionally use 99.9% simple substance silver as negative electrode, described silver-colored plasma body refers to the silver-colored plasma body that 99.9% silver-colored simple substance forms.
The injection order of nitrogen plasma and silver-colored plasma body does not limit, and injects silver-colored plasma body after can first injecting nitrogen plasma, injects nitrogen plasma after also can first injecting silver-colored plasma body, also can inject nitrogen plasma and silver-colored plasma body simultaneously.
Described medical macromolecular materials comprise film, woven and the non-woven fabrics that polyethylene, polypropylene, tetrafluoroethylene, polyvinylidene difluoride (PVDF), polyvinyl acetate (PVA), poly(lactic acid), polyhydroxyalkanoate, polyethylene terephthalate, Mierocrystalline cellulose etc. are made.
Described anti-infection property refers to that medical use anti-infection polymer surface reaches more than 90% the anti-infective rate of bacterium; Bacterial species comprises intestinal bacteria, streptococcus aureus, staphylococcus epidermidis, Pseudomonas aeruginosa, Candida albicans, streptococcus pneumoniae, klebsiella, blackish green coccus.
The present invention has following beneficial effect:
1, the present invention utilizes N
2and/or NH
3plasma body injects nitrogen plasma to medical macromolecular materials, and nitrogen plasma and medical macromolecular materials surface reaction, produce nitrogenous organo-functional group, makes material have the Growth and reproduction effect of anti-bacteria.
2, the present invention also utilizes silver-colored plasma body to inject silver ions to medical macromolecular materials surface, and not only the restraining effect of the Growth and reproduction to bacterium, even has killing action to bacterium, has further improved the anti-infective performance of medical macromolecular materials.
3, the present invention is simple to operate, does not affect the physical chemistry structure of material body.
4, the medical use anti-infection polymer surface Stability Analysis of Structures that the present invention obtains after processing, has anti-infective performance long-acting, wide spectrum.
Brief description of the drawings
Fig. 1 is the Antiinfection polyethylene non-woven fabrics that embodiment 1 makes;
Fig. 2 is the Antiinfection polyethylene non-woven fabrics that makes of embodiment 1 and the growth and breeding situation map of the material streptococcus aureus without the inventive method processing;
Fig. 3 is the Antiinfection polyethylene nonwoven surface silver that utilizes XPS to make embodiment 1, the depth profile that nitrogen plasma injects;
Fig. 4 is the surface chemical structure figure that utilizes the Antiinfection polyethylene non-woven fabrics that embodiment 1 is made of XPS acquisition.
Fig. 5 is that the polyethylene nonwoven surface that Escherichia coli Growth makes at embodiment 2 is cultivated the growth and breeding situation after 24 hours.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further described.
Embodiment 1
Adopt plasma technology to prepare the method for medical use anti-infection macromolecular material, comprise the following steps:
(1) be that 1.0mm, size are positioned in sample table for 5.0cm × 10.0cm medical polyethylene non-woven fabrics by thickness, using 99.9% silver medal as electrode, silver electrode is contained on the plasma cathode arc of plasma apparatus, then sealing equipment vacuum chamber, and vacuumize;
(2) when vacuum tightness is 1 × 10
-5when Pa, pass into the argon gas of 20.0SCCM, open radio frequency plasma body source, power is 1000W, generates argon plasma, allows polyethylene non-woven fabrics in argon plasma, soak 1 minute;
(3) argon flow amount is adjusted to 5.0SCCM, pass into the nitrogen of 20.0SCCM, generate nitrogen plasma, open the pulsed negative bias in sample table, pulsewidth is 300 μ s simultaneously, and frequency is 30Hz, voltage is-5kv, nitrogen plasma is injected to polyethylene nonwoven surface, inject the degree of depth and can reach 1.2 μ m, implantation dosage reaches 1 × 10
15ions/cm
2time, turn off nitrogen;
(4) keep argon flow amount 5.0SCCM, open silver-colored plasma cathode arc, cathode arc pulsewidth is 300 μ s, frequency is 30Hz, and electric current is 1.0A, and silver-colored plasma body is injected to polyethylene nonwoven surface, inject the degree of depth and can reach 1.2 μ m, silver ions implantation dosage reaches 1 × 10
17ions/cm
2time, turn off cathode arc and radio-frequency plasma power supply;
(5) take out polyethylene non-woven fabrics, obtain Antiinfection polyethylene non-woven fabrics.
Fig. 1 is the Antiinfection polyethylene non-woven fabrics that embodiment 1 makes.
The polyethylene non-woven fabrics that embodiment 1 is made is tested, and as shown in Figure 2, can find out on the polyethylene non-woven fabrics that embodiment 1 makes and almost can't see streptococcus aureus, and it is 1 × 10 to concentration
4the antibiotic rate of the streptococcus aureus of CFU/ml is 99.9%.
Fig. 3 is the polyethylene nonwoven surface silver that utilizes XPS to make embodiment 1, the depth profile that nitrogen injects; The injection degree of depth that can find out silver, nitrogen reaches respectively 1.2 μ m, and silver element and nitrogen element are injected into the upper layer of polyethylene non-woven fabrics, and are not only to rest on outside surface.
Fig. 4 is the surface chemical structure figure that utilizes the polyethylene non-woven fabrics that embodiment 1 is made of XPS acquisition; Can find out and form N-C, N ≡ C, N-C=O on the surface of polyethylene non-woven fabrics.
Embodiment 2
Adopt plasma technology to prepare the method for medical use anti-infection macromolecular material, comprise the following steps:
(1) be that 0.5mm, size are positioned in sample table for 10.0cm × 10.0cm medical polyethylene non-woven fabrics by thickness, then sealing equipment vacuum chamber, and vacuumize;
(2) when vacuum tightness is 8 × 10
-4when Pa, pass into the argon gas of 10.0SCCM, open radio frequency plasma body source, power is 1000W, generates argon plasma, allows polyethylene non-woven fabrics in argon plasma, soak 50 minutes;
(3) argon flow amount is adjusted to 3.0SCCM, and pass into the nitrogen of 20.0SCCM, generate nitrogen plasma, open the pulsed negative bias in sample table, pulsewidth is 300 μ s simultaneously, and frequency is 30Hz, voltage is-0.5kv, nitrogen plasma is injected to polyethylene nonwoven surface, inject the degree of depth and can reach 0.001 μ m, implantation dosage reaches 5 × 10
22ions/cm
2time, turn off nitrogen and radio-frequency plasma power supply;
(4) take out polyethylene non-woven fabrics, obtain Antiinfection polyethylene non-woven fabrics.
Fig. 5 is that the Antiinfection polyethylene nonwoven surface that intestinal bacteria make at embodiment 2 is cultivated the growth and breeding situation after 24 hours; From figure, can obviously find out, the intestinal bacteria quantity on Antiinfection polyethylene non-woven fabrics after treatment is far fewer than polyethylene non-woven fabrics quantity before treatment.
Embodiment 3
Adopt plasma technology to prepare the method for medical use anti-infection macromolecular material, comprise the following steps:
(1), on the fixing treatment bench of the polypropylene film that is 0.05mm by thickness, using 99.9% silver medal as electrode, be contained on the cathode arc of plasma apparatus, then sealing equipment vacuum chamber, and vacuumize;
(2) when vacuum tightness is 1 × 10
-3when Pa, pass into the argon gas of 10.0SCCM, open radio frequency plasma body source, power is 800W, generates argon plasma, allows polypropylene film in argon plasma, soak 10 minutes;
(3) argon flow amount is adjusted to 3.0SCCM, and pass into the nitrogen of 10.0SCCM, generate nitrogen plasma, open the pulsed negative bias in sample table, pulsewidth is 300 μ s simultaneously, and frequency is 30Hz, voltage is-20kv, nitrogen plasma is injected to polypropylene film, inject the degree of depth and can reach 3 μ m, implantation dosage reaches 1 × 10
22ions/cm
2time, turn off nitrogen;
(4) keep argon flow amount 3.0SCCM, open silver-colored plasma cathode arc, cathode arc pulsewidth is 300 μ s, and frequency is 30Hz, and electric current is 1.0A, and silver-colored plasma body is injected to polypropylene film, injects the degree of depth and can reach 3 μ m, and silver ions implantation dosage reaches 1 × 10
19ions/cm
2time, turn off cathode arc and radio-frequency plasma power supply;
(5) take out polypropylene film, obtain anti-infective polypropylene film.
Embodiment 4
Adopt plasma technology to prepare the method for medical use anti-infection macromolecular material, comprise the following steps:
(1), on the fixing treatment bench of the polyvinyl acetate (PVA) film that is 0.02mm by thickness, using 99.9% silver medal as electrode, be contained on the cathode arc of plasma apparatus, then sealing equipment vacuum chamber, and vacuumize;
(2) when vacuum tightness is 5 × 10
-4when Pa, pass into the argon gas of 5.0SCCM, open radio frequency plasma body source, power is 1200W, generates argon plasma, allows polyvinyl acetate (PVA) film in argon plasma, soak 100 minutes;
(3) keep argon flow amount 5.0SCCM, pass into the nitrogen of 10.0SCCM, generate nitrogen plasma, open the pulsed negative bias in sample table, pulsewidth is 300 μ s simultaneously, and frequency is 30Hz, voltage is-2kv, nitrogen plasma is injected to polyvinyl acetate (PVA) film, inject the degree of depth and can reach 0.5 μ m, implantation dosage reaches 1 × 10
17ions/cm
2time, turn off nitrogen;
(4) keep argon flow amount 5.0SCCM, open silver-colored plasma cathode arc, cathode arc pulsewidth is 300 μ s, frequency is 30Hz, and electric current is 1.0A, and silver-colored plasma body is injected to polyvinyl acetate (PVA) film, inject the degree of depth and can reach 0.5 μ m, silver ions implantation dosage reaches 5 × 10
19ions/cm
2time, turn off cathode arc and radio-frequency plasma power supply;
(5) take out polyvinyl acetate (PVA) film, obtain anti-infective polyvinyl acetate (PVA) film.
Embodiment 5
Adopt plasma technology to prepare the method for medical use anti-infection macromolecular material, comprise the following steps:
(1) be in 0.05mm, the big or small sample table being positioned over for 10.0cm × 10.0cm poly(lactic acid) non-woven fabrics by thickness, using 99.9% silver medal as electrode, silver electrode is contained on the plasma cathode arc of plasma apparatus, then sealing equipment vacuum chamber, and vacuumize;
(2) when vacuum tightness is 1 × 10
-5when Pa, pass into the argon gas of 10.0SCCM, open radio frequency plasma body source, power is 1000W, generates argon plasma, allows poly(lactic acid) non-woven fabrics in argon plasma, soak 0.06 minute;
(3) argon flow amount is adjusted to 5.0SCCM, open silver-colored plasma cathode arc, cathode arc pulsewidth is 200 μ s, and frequency is 40Hz, electric current is 1.0A, open the pulsed negative bias in sample table, pulsewidth is 200 μ s simultaneously, and frequency is 40Hz, voltage is-30kv, the silver-colored plasma body generating is injected to poly(lactic acid) nonwoven surface, inject the degree of depth and can reach 2 μ m, silver ions implantation dosage reaches 1 × 10
13ions/cm
2time, turn off cathode arc;
(4) keep argon flow amount 5.0SCCM, pass into the NH of 30.0SCCM
3, generate nitrogen plasma, nitrogen plasma is injected to poly(lactic acid) nonwoven surface, inject the degree of depth and can reach 3 μ m, implantation dosage reaches 1 × 10
20ions/cm
2time, turn off nitrogen and radio-frequency plasma power supply;
(5) take out poly(lactic acid) non-woven fabrics, obtain anti-infective poly(lactic acid) non-woven fabrics.
Embodiment 6
Adopt plasma technology to prepare the method for medical use anti-infection macromolecular material, comprise the following steps:
(1) be that 0.05mm, size are positioned in sample table for 10.0cm × 10.0cm polyethylene terephthalate non-woven fabrics by thickness, using 99.9% silver medal as electrode, on plasma cathode arc, then sealing equipment vacuum chamber, and vacuumize;
(2) when vacuum tightness is 1 × 10
-5when Pa, pass into the argon gas of 10.0SCCM, open radio frequency plasma body source, power is 1000W, generates argon plasma, allows polyethylene terephthalate non-woven fabrics in argon plasma, soak 5 minutes;
(3) argon flow amount is adjusted to 5.0SCCM, and pass into the nitrogen of 30.0SCCM, generate nitrogen plasma, open the pulsed negative bias in sample table, pulsewidth is 200 μ s simultaneously, and frequency is 40Hz, voltage is-30kv, nitrogen plasma is injected to polyethylene terephthalate nonwoven surface, inject the degree of depth and can reach 0.3 μ m, implantation dosage reaches 1 × 10
20ions/cm
2time, turn off nitrogen;
(4) keep argon flow amount 5.0SCCM, open silver-colored plasma cathode arc, cathode arc pulsewidth is 200 μ s, frequency is 40Hz, electric current is 1.0A, again the silver-colored plasma body generating is injected to polyethylene terephthalate nonwoven surface, inject the degree of depth and can reach 0.001 μ m, silver ions implantation dosage reaches 1 × 10
14ions/cm
2time, turn off cathode arc and radio-frequency plasma power supply;
(5) take out polyethylene terephthalate non-woven fabrics, obtain anti-infective polyethylene terephthalate non-woven fabrics.
Embodiment 7
Adopt plasma technology to prepare the method for medical use anti-infection macromolecular material, comprise the following steps:
(1) be that 0.2mm, size are positioned in sample table for 10.0cm × 10.0cm cellulosic textile fabric by thickness, using 99.9% silver medal as electrode, silver electrode is contained on plasma cathode arc, then sealing equipment vacuum chamber, and vacuumize;
(2) when vacuum tightness is 8 × 10
-3when Pa, pass into the argon gas of 5.0SCCM, open radio frequency plasma body source, power is 1500W, generates argon plasma, allows cellulosic textile fabric in argon plasma, soak 120 minutes;
(3) argon flow amount is adjusted to 5.0SCCM, passes into the nitrogen of 10.0SCCM, generate nitrogen plasma; Open silver-colored plasma cathode arc, cathode arc pulsewidth is 200 μ s, frequency is 40Hz, and electric current is 1.0A, opens the pulsed negative bias in sample table simultaneously, pulsewidth is 250 μ s, frequency is 30Hz, and voltage is-10kV that nitrogen plasma and silver-colored plasma body are injected to cellulosic textile fabric surface, inject the degree of depth and can reach 1 μ m, when nitrogen implantation dosage reaches 5 × 10
18ions/cm
2time, turn off nitrogen, when silver ions implantation dosage reaches 5 × 10
19ions/cm
2after, turn off cathode arc and radio-frequency plasma power supply;
(4) take out this cellulosic textile fabric, obtain anti-infectious fiber element yarn fabric.
Embodiment 8
Adopt plasma technology to prepare the method for medical use anti-infection macromolecular material, comprise the following steps:
(1) polytetrafluoroethylene film that is 0.1mm by thickness is fixed on treatment bench, using 99.9% silver medal as electrode, is contained on the cathode arc of plasma apparatus, and then sealing equipment vacuum chamber, and vacuumize;
(2) when vacuum tightness is 2 × 10
-3when Pa, pass into the argon gas of 40.0SCCM, open radio frequency plasma body source, power is 800W, generates argon plasma, allows polytetrafluoroethylene film in argon plasma, soak 10 minutes;
(3) argon flow amount is adjusted to 3.0SCCM, and pass into the nitrogen of 20.0SCCM, generate nitrogen plasma, open the pulsed negative bias in sample table, pulsewidth is 300 μ s simultaneously, and frequency is 30Hz, voltage is-20kv, nitrogen plasma is injected to polytetrafluoroethylene film, inject the degree of depth and can reach 3 μ m, implantation dosage reaches 1 × 10
22ions/cm
2time, turn off nitrogen;
(4) keep argon flow amount 3.0SCCM, open silver-colored plasma cathode arc, cathode arc pulsewidth is 300 μ s, frequency is 30Hz, and electric current is 1.0A, and silver-colored plasma body is injected to polytetrafluoroethylene film, inject the degree of depth and can reach 1.8 μ m, silver ions implantation dosage reaches 1 × 10
19ions/cm
2time, turn off cathode arc and radio-frequency plasma power supply;
(5) take out polytetrafluoroethylene film, obtain anti-infective polytetrafluoroethylene film.
Embodiment 9
Adopt plasma technology to prepare the method for medical use anti-infection macromolecular material, comprise the following steps:
(1) on the fixing treatment bench of the polyvinylidene difluoride (PVDF) non-woven thin-film that is 0.05mm by thickness, then sealing equipment vacuum chamber, and vacuumize;
(2) when vacuum tightness is 1 × 10
-2when Pa, pass into the argon gas of 40.0SCCM, open radio frequency plasma body source, power is 800W, generates argon plasma, allows polyvinylidene difluoride film in argon plasma, soak 10 minutes;
(3) argon flow amount is adjusted to 3.0SCCM, and pass into the nitrogen of 20.0SCCM, generate nitrogen plasma, open the pulsed negative bias in sample table, pulsewidth is 300 μ s simultaneously, and frequency is 30Hz, voltage is-10kv, nitrogen plasma is injected to polyvinylidene difluoride film, inject the degree of depth and can reach 2 μ m, implantation dosage reaches 1 × 10
22ions/cm
2time, turn off nitrogen;
(4) take out polyvinylidene difluoride film, obtain anti-infective polyvinylidene difluoride film.
Embodiment 10
Adopt plasma technology to prepare the method for medical use anti-infection macromolecular material, comprise the following steps:
(1) be that 0.5mm, size are positioned in sample table for 10.0cm × 10.0cm polyhydroxyalkanoate non-woven fabrics by thickness, using 99.9% silver medal as electrode, on plasma cathode arc, then sealing equipment vacuum chamber, and vacuumize;
(2) when vacuum tightness is 1 × 10
-5when Pa, pass into the argon gas of 5.0SCCM, open radio frequency plasma body source, power is 500W, generates argon plasma, allows polyhydroxyalkanoate non-woven fabrics in argon plasma, soak 1 minute;
(3) argon flow amount is adjusted to 5.0SCCM, and pass into ammonia and the 15.0SCCM nitrogen of 15.0SCCM, generate nitrogen plasma, open the pulsed negative bias in sample table, pulsewidth is 200 μ s simultaneously, and frequency is 40Hz, voltage is-30kv, nitrogen plasma is injected to polyhydroxyalkanoate nonwoven surface, inject the degree of depth and can reach 3 μ m, implantation dosage reaches 1 × 10
17ions/cm
2time, turn off nitrogen;
(4) keep argon flow amount 5.0SCCM, open silver-colored plasma cathode arc, cathode arc pulsewidth is 200 μ s, frequency is 40Hz, electric current is 1.0A, again the silver-colored plasma body generating is injected to polyhydroxyalkanoate nonwoven surface, inject the degree of depth and can reach 1.0 μ m, silver ions implantation dosage reaches 1 × 10
13ions/cm
2time, turn off cathode arc and radio-frequency plasma power supply;
(5) take out polyhydroxyalkanoate non-woven fabrics, obtain anti-infective polyhydroxyalkanoate non-woven fabrics.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give exhaustive to all embodiments.Everyly belong to apparent variation or the still row in protection scope of the present invention of variation that technical scheme of the present invention extends out.
Claims (2)
1. adopt plasma technology to prepare the method for medical use anti-infection macromolecular material, it is characterized in that, comprise the following steps:
(1) be 1.0 × 10 at sealed vacuum degree
-2～1.0 × 10
-5under Pa condition, medical macromolecular materials are placed in to argon plasma 0.001～2 hour;
(2) nitrogen plasma is injected into medical macromolecular materials surface, reacts with macromolecular chain, generate nitrogenous functional group, obtain medical use anti-infection macromolecular material;
Wherein, described nitrogen plasma is N
2and/or NH
3there is the nitrogen plasma that plasma bodyization generates;
The implantation dosage of nitrogen plasma is 1.0 × 10
15～5.0 × 10
22ions/cm
2, injecting the degree of depth is 0.001～3 μ m;
Described step (2) also comprises that silver, as electrode, injects medical macromolecular materials surface by silver-colored plasma body; The implantation dosage of silver plasma body is 1.0 × 10
13～5.0 × 10
19ions/cm
2, injecting the degree of depth is 0.001～3 μ m.
2. employing plasma technology according to claim 1 is prepared the method for medical use anti-infection macromolecular material, it is characterized in that, described medical macromolecular materials comprise film, woven and the non-woven fabrics that polyethylene, polypropylene, tetrafluoroethylene, polyvinylidene difluoride (PVDF), polyvinyl acetate (PVA), poly(lactic acid), polyhydroxyalkanoate, polyethylene terephthalate, Mierocrystalline cellulose are made.
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| CN104817711B (en) * | 2015-04-14 | 2018-03-02 | 中国人民解放军第三军医大学第二附属医院 | The antibiotic property method of modifying of silicon rubber |
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| "等离子体法制备抗感染医用高分子材料的研究";张维;《中国优秀硕博学士论文》;20110525;第111,119-120,126页 * |
| "银离子注入表面改性涤纶材料的抗菌性能研究";李建新等;《真空科学与技术学报》;20061031;第26卷(第5期);第408-411页 * |
| 张维."等离子体法制备抗感染医用高分子材料的研究".《中国优秀硕博学士论文》.2011,第111,119-120,126页. * |
| 李建新等."银离子注入表面改性涤纶材料的抗菌性能研究".《真空科学与技术学报》.2006,第26卷(第5期),第408-411页. * |
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