CN101437977A - Antimicrobial coating methods - Google Patents
Antimicrobial coating methods Download PDFInfo
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- CN101437977A CN101437977A CNA2007800103843A CN200780010384A CN101437977A CN 101437977 A CN101437977 A CN 101437977A CN A2007800103843 A CNA2007800103843 A CN A2007800103843A CN 200780010384 A CN200780010384 A CN 200780010384A CN 101437977 A CN101437977 A CN 101437977A
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Abstract
The invention is directed to efficient methods for depositing highly adherent anti not microbial materials onto a wide range of surfaces. A controlled cathodic arc process is described, which results in enhanced adhesion of silver oxide to polymers and other surfaces, such as surfaces of medical devices. Deposition of anti-microbial materials directly onto the substrates is possible in a cost-effective manner that maintains high anti-microbial activity over several weeks when the coated devices are employed in vivo.
Description
The application requires the U.S. Provisional Application sequence number No.60/762 of submission on January 27th, 2006,769, the U.S. Provisional Application sequence number No.60/763 that submitted on January 30th, 2006,262, the U.S. Provisional Application sequence number No.60/776 that submitted on February 25th, 2006,537, the U.S. Provisional Application sequence number No.60/779 that submitted on March 6th, 2006,917 right of priority, the disclosure of these provisional application files is incorporated into this for your guidance.The application is the U.S. Patent Application Serial Number No.10/741 that submitted on December 18th, 2003,015 (it requires the U.S. Provisional Application sequence number No.60/434 that submitted on December 18th, 2002,784 right of priority) part continuation application, and its disclosed content is incorporated into this for your guidance.
Technical field
The present invention relates to be used to make cathode arc ion plasma (ion plasma) depositing operation of the metallic coating of modification, the metallic coating of this modification is used on the surface of the device that is used for medical applications and material and forms the germ resistance surface.Especially, the present invention relates to a kind of technology that is used at highly controlled condition deposit silver (Ag) and other germ resistance metals or their composition, have the adhesivity of improvement and in the time period that prolongs, keep active antiseptic paint with formation.
Background technology
Verified metal is as the sterilization idiocratic of silver, zinc, niobium, tantalum, hafnium, zirconium, titanium, chromium, nickel, copper, platinum and gold.In these metals, the silver of ion or compound form is to be widely known by the people most and the most widely used germ resistance metal.Simple substance silver (elemental silver) has certain germ resistance advantage, but it uses inoperative for most of germ resistancies usually.As the oxide compound to silver carry out coating and be coated with China ink cause they reactive behavior and the observation of deliquescent reduction shown in, it is believed that the silver of oxidised form has more activity as antibiont.
People have attempted to utilize the generally acknowledged chemical process based on solution, are used for improving silver-colored reactivity by the oxide compound of silver and the making of composition of silver and other materials.U.S. Patent No. 4,828,832 have described such as the argent salts solution of Silver Nitrate salt brine solution and oxygenant such as benzoyl peroxide and have been combined in the application of treatment skin in infecting.
U.S. Patent No. 5,824,267 have disclosed on the surface of plastics and have embedded silver metal particles and pottery or alkali metal particles to give the plastics antimicrobial characteristic.Ultrafine silver metal particles obtains from the silver metal salt brine solution by chemical deposition.
Can provide silver although produce silver-colored particulate solution methods with anti-microbial activity, very little to the control of the silver-colored grain pattern that obtains, so these methods are limited in their application.And, such as some ionic species of silver nitrate aqueous solution, because potential to the pungency of skin, so be hyperactivity for great majority are used, therefore must carefully be monitored and be controlled.Another problem based on the chemical process of solution is to form stable composition under the situation that does not produce harmful side product.The silver ions that is attached in slurry, coating, polymkeric substance or the gel trends towards having short shelf life, in part because that take place and side reactions various components in the solution based on water.
There is tangible demand for the germ resistance surface that can produce the release of germ resistance metal ion persistence.The surface energy that produces the release of germ resistance ionic persistence is useful especially in operation and wound dressing and bandage, operating sutures, conduit and other medical treatment devices, implant, dummy (prosthetics), oral application thing (dental application) and tissue regeneration.Other devices that also can benefit from the lasting release of anti-bacterial material comprise: medical instruments and surface, surface, restaurant (restaurant surface), face shield, clothes, keeper and other fixtures, swimming pool, hot basin (hot tub), tap water strainer, cooling system, porous hydrophilic material, humidifier and air conditioning system.
In U.S. Patent No. 4,886, the method that the persistence that is used to produce metal ion discharges has been described in 505.According to this method, use such as first metal of silver and this device of second washing that is connected in first metal by switch (switch) such as platinum.In the presence of body fluid, the existence of silver metal and platinum has caused generation galvanic effect (galvanicaction), and it is used for discharging or disengaging silver ions.Discharge by controlling ionic at the switch of device peripheral operation.
The technology that applies electric current in wound dressings that applies silver or medical treatment device also is a U.S. Patent No. 4,219,125 and No.4, and 411,648 theme.Although the use of external switch controller or foreign current can improve the speed that metal ion discharges, this peripheral control unit or electric current are not to be feasible to various application.
U.S. Patent No. 6,365,220 have described to be used to make and a kind ofly provide persistence to discharge the germ resistance ion and need not the method that foreign current is kept the germ resistance surface of this release.According to this disclosure content, by sputter or evaporation technology, with the multiple layer metal thin film deposition on matrix (substrate).By using different metal composites, and adopt etching technique so that the surface roughening of layer or have texture can produce multiple microbedding (microlayer) interface at different layers.When being exposed to body fluid, multiple interface can provide ionic to discharge by galvanic couple and non-galvanic effect.
U.S. Patent No. 5,837,275 have also disclosed the germ resistance ionic antiseptic paint that lasting release is provided.Prepare coating by the sputtering technology that utilizes the particular deposition parameter.Coating is described to present the metallic film of " atom is mixed and disorderly ", and claims that its lasting release for metal ion is necessary.
It is said Tetrasilver tetroxide (Ag
4O
4) orderly monocrystalline can be used for treating skin disease (U.S. Patent No. 6,258,385) as antiseptic-germicide.But except that local the use, this mixture is also impracticable, and it can (that is, some days) provide the ability of the lasting release of anti-bacterial material also not to be confirmed in over a long time.
Usually, the deposition of anti-bacterial material is limited to of three kinds of peculiar methods being used for preparing silver and silver suboxide coating.In these methods each all has important disadvantages, and does not have a kind of being developed to can prepare the germ resistance film that has high-adhesiveness and be evenly distributed on the surface of medical treatment device and apparatus effectively.Normally used process condition such as sputter, dipping and ion beam assisted depositing, is prepared for flexible substrate or elastic devices and is had limited adhering coating.In a large amount of treatment time of cost, in order to increase adhesive power, extra layer is necessary sometimes.
By cathode arc metallic substance is deposited on the matrix in a vacuum and is well known in the art.Contrast other plasma evaporation deposition method, ion plasma deposition (IPD) can prepare highly purified intensive polycomponent coating, described at U.S. Patent Application Publication No. No.2004/0185182.But traditional cathodic arc deposition method has some shortcoming.Because target material invalid used and lacks the waste that particle control has caused expensive material.Lack the formation that the control for the treatment of deposition material has caused particles of different sizes, this has just caused the deposition of non-uniform coating.Usually, cathode arc technology also requires matrix surface is heated to very high temperature, and this can destroy body material, and has seriously limited the selection of matrix.
Summary of the invention
The present invention has satisfied for can being bonded to arbitrary surfaces, and has controlled release rate and life-span, and is the needs that continue of nontoxic anti-bacterial material in required application.As described in the invention, can utilize new cathode arc IPD depositing operation, the antiseptic paint that will have these characteristics is deposited on the multiple matrix surface.
The purpose of this invention is to provide a kind of by utilizing ion plasma deposition technology that anti-bacterial material is deposited on the matrix, to form the method for discrete germ resistance granular layer.
Further aim of the present invention provides a kind of method that is used for preparing the germ resistance surface on any product of finishing, and has therefore eliminated the needs that adopt complicated chemistry, slurrying, coating and adhesive bonding technique (bonding technology).
Another object of the present invention provides the germ resistance surface, and it in the time period that prolongs, provides the antiseptic-germicide that continues release with the treatment level of significance in vivo.
Another object of the present invention is the lasting release for metal ion, provides the germ resistance surface by dispersive (dispersed) metal of one or more elements and/or metal/metal oxide are injected (impregnating) or be deposited into matrix.
Therefore, in particularly preferred embodiments, the invention provides deposition, infiltration or the shop layer (layering) of silver and other metal ions, described silver and other metal links (combination) to nano level, ultra micro meter level, reach the solid-state structure (it is designed to be dispersed to the composition of the unit price in the surface or on it, two valency and multivalence oxide compound) of micron order crystalline metal and metal oxide.Activity owing to enzyme can discharge negatively charged ion by contacting with pathogenic agent then, perhaps contacts by interpolation water or with body fluid to discharge negatively charged ion.
Disclosed technology can be used in the manufacturing of various devices of a kind of controllable groups compound of needs, but be specially adapted to need germ-resistant, sterilization, small area biocidal or antimicrobial surface to very large-area scroll (roll), such as bandage, or parts independently, such as conduit, do the manufacturing of axle (stem) or implant.This technology formed to will with quantity, particle size and the control of energy of Ionized oxygen or other gas bonded ionized material, and can be applicable to unit price, two valency, and the broad range of the combination of multivalence oxide compound and nitride and a plurality of layers.
This technology can be used for making antibacterial products or existing procucts and starting material is carried out surface treatment.The energy device that this technology can be used to produce small dimension (scale) is to improve anti-microbial activity or to provide energy (power) for other nanotechnology device; For example, silver oxide cell is that Micropump, implant, galvanic couple surface (galvanic surface) and other need the device of energy that energy is provided.
Therefore, one aspect of the present invention provides a kind of method that is used for deposition germ resistance surface on matrix, may further comprise the steps: the negative electrode target that will comprise potential antimicrobial metal is placed in the vacuum chamber, provide power to produce electric arc on negative electrode to negative electrode, it is the plasma body of ionized particles with the ionization of negative pole metal; To introduce vacuum chamber such as the reactant gas of oxygen, so that make this gas and ionized plasma particles react, and by in depositing operation with a kind of controllable mode move matrix near or further away from each other target control the deposition of plasma particle on matrix.
Means by control electric arc can realize the further control of depositing operation, thus, regulate the power that is fed on the negative pole to change the speed that electric arc produces.
Another aspect of the present invention is that the germ resistance that comprises metal oxide particle dispersion surface is provided on matrix, and wherein, metal is selected from by silver, nickel, zinc, copper, gold, platinum, niobium, tantalum, hafnium, zirconium, titanium, chromium, and the group formed of their combination.
The present invention relates to a kind of technology that on selected body material, deposits anti-bacterial material.This matrix can be an any materials, such as metal, pottery, plastics, glass, flexible sheets (flexible sheet), porous paper, pottery or their combination.Although matrix can comprise any in the multiple device, preferred especially medical treatment device.These medical treatment devices comprise conduit, implant, support, tracheal catheter, orthopedic pin (orthopedic pin), splitter, flow diverter, prosthetic device, tooth implant, dressing and wound closure (woundclosures).Yet, should be appreciated that the present invention is not limited to these devices, can extend to the device that other are used for medical field, such as face shield, clothes, operational tool and surface (surface).
About implanting to infect two important factors are arranged: the introducing of bacterium in the implant surgery process; And the skin openings after the operation.Transcutaneous device (transdermal device) is main infected zone.Because device is separated with skin, between skin and device, formed the slit, bacterial contamination has just taken place.
Another aspect of the present invention relates to and is used for tuned (tuned) germ resistance surface or other composition are provided to the improved and more economical method that is used for human body and beasts medical treatment device and other application.
Anti-bacterial material can be any solid material or the combination with material of antimicrobial characteristic.Preferable material is the metal with potential antimicrobial characteristic and biocompatibility (that is, not being damaged in the purpose environment).These metals comprise silver, zinc, niobium, tantalum, hafnium, zirconium, titanium, chromium, nickel, copper, platinum and gold (being also referred to as " germ resistance metal " in this article).Term " potential antimicrobial characteristic " refers to this situation: the metal of these simple substance forms is not had reactive behavior usually, so that can not be as effective antibiont.Yet, after this metal is ionized, have stronger antibacterial effect.Therefore, after implementing metal ionization, this germ resistance metal has the potential antimicrobial characteristic.During ionization, the germ resistance metal also can with various reactant gases for example nitrogen or combination with oxygen, forming nitride, oxide compound, and/or the compound of their combination.
Definition
Ion plasma deposition is a kind of by utilizing cathode arc to discharge on target material, and produces the method for energetic plasma.
Cathode arc is also referred to as vacuum arc, is a kind of device that is used for producing from solid metal plasma body.The electric arc collision is on metal, and the high-energy-density of electric arc makes this evaporation of metal and ionization, has produced the plasma body of sustained arc.Vacuum arc is different with high-voltage arc, because metal vapors itself is Ionized, rather than environmental gas.
Huge or macroparticle is greater than single ionic particle; Millimicro (or little) particle is the particle that size is about 100 nanometers; Medium big particle is that 100 nanometers are to about 1 micron; Very big particle is the particle greater than 1 micron.
When enough strong energy destroys atomic group when (such as gas group, object or target), COULOMB EXPLOSION then takes place, the electric field of the energy orders about some or all electronics and leaves atom like this.If there has not been electronics, ionic group can be blasted because of the coulomb repulsion of positive charge.
Plasma gas phase deposition (PVD) is the technology of deposit film in gas phase, and wherein source material physically is transformed on the matrix in a vacuum, and does not relate to any chemical reaction.Such deposition comprises thermal evaporation electron beam deposition and sputtering sedimentation.IPD technology is the subtype of physical vapor deposition.
Term used herein " medical treatment device " is in order to extend to employed all devices in the medical field widely, to comprise support, conduit, various implants etc., and regardless of the material of making it.The medical treatment device that relates to herein and other medical reference substances are understood that also to comprise that the animal doctor uses device and application.
Term " potential antimicrobial characteristic " is meant this situation: promptly, the metal of these simple substance forms is not had reactive behavior usually, so that can not be as effective antibiont, but may, after being ionized, this metal shows stronger antibacterial effect.Therefore, be implemented in many cases after the metal ionization, this germ resistance metal has the potential antimicrobial characteristic.During ionization, the germ resistance metal also can with various reactant gases for example nitrogen or combination with oxygen, forming nitride, oxide compound, and/or the compound of their combination.
" many valencys " used herein is meant one or more valency forms, and is appreciated that electric charge that is meant on the ion or the electric charge that is assigned to specific ion based on its electronic state (electronic state).
Unless otherwise indicated, silver suboxide is defined as the singlet form of silver suboxide (AgO).
Term " about " used herein is in order to illustrate that concrete number does not need accurately, and concrete process or the method that can pass through to be adopted decide, and this number can be higher or on the low side.
The PEEK-polyether-ether-ketone
The PTFE-tetrafluoroethylene
The EPIFE-expanded polytetrafluoroethyl(ne
UNMWPE is a ultrahigh molecular weight polyethylene(UHMWPE)
It should be understood that " one " that is used to limit claim is not that necessity is limited to a single material.
Description of drawings
Fig. 1 is the sketch of IPD equipment.1. target material, 2. coated matrix, 3. be used for mobile matrix near or away from the mechanism of target, 4. vacuum chamber, and 5. power supplys that are used for target.
Fig. 2 is another embodiment of IPD equipment.1. target material, 2. coated matrix, 3. have mobile matrix near or away from the mechanism of target ability, the power supply of 4. vacuum chamber, and 5. targets, 6. the electric arc controller of decision arc speed.
Embodiment
The invention provides the advantage that some are better than this area antiseptic paint and are used to deposit other states of antiseptic paint technology, comprising: controllably discharge, make coating embed in the matrix, for the lower operating temperature of some material, than turnout, the measurability of the traditional remarkable improvement of cathode arc technology on working (machining) efficiency and can be applicable to the more body material of wide region.
In addition, obtain the good coating of utilizing traditional IPD method to be difficult to obtain, comprised silver suboxide, cupric oxide and hafnium nitride coating.Than more expensive method (such as in U.S. Patent No. 5,454, generalized in 886, it is introduced therewith as a reference), under suitable thickness, these materials have higher anti-microbial activity.Therefore, by adopting new method, can realize having the thinner coating and the shorter treatment time of identical antibiotic effect based on IPD.Higher turnout is possible, and it can cause the saving of production cost, and especially this is very significant advantage for medicine industry.
The factor of giving the film that utilizes disclosed technology and obtain with this superiority is to find new IPD technology to have produced the sedimentary increase of heavy ion (but not reduction) in fact it improved the quality of film.For many years for technicians, in the use of conventional cathode arc deposited technology, the most significant trend is to reduce oarse-grained deposition, so that produce cleaner and more uniform film.Understanding traditional in the industry is that macrobead is disadvantageous for the quality of deposit film usually.
The present invention relates to a kind of technology that on selected body material, deposits anti-bacterial material.This matrix can be an any materials, such as metal, pottery, plastics, glass, flexible sheets, porous paper, pottery or their combination.Although matrix can comprise any in the multiple device, preferred especially medical treatment device.These medical treatment devices comprise conduit, implant, support, tracheal catheter, orthopedic pin, splitter, flow diverter, prosthetic device, tooth implant, dressing and wound closure (wound closures).Yet, should be appreciated that the present invention is not limited to these devices, can extend to the device that other are used for medical field, such as face shield, clothes, operational tool and surface.
About implanting to infect two important factors are arranged: the introducing of bacterium in the implant surgery process; And the skin openings after the operation.Transcutaneous device (transdermal device) is main infected zone.Because device is separated with skin, between skin and device, formed the slit, bacterial contamination has just taken place.
Another aspect of the present invention relates to being used for tuned germ resistance surface or other composition be provided to and is used for improvement that human body and beasts medical treatment device and other use and more economical method.Anti-bacterial material can be any solid material or the combination with material of antimicrobial characteristic.Preferable material is the metal with potential antimicrobial characteristic and biocompatibility (that is, not being damaged in the purpose environment).These metals comprise silver, zinc, niobium, tantalum, hafnium, zirconium, titanium, chromium, nickel, copper, platinum and gold (being also referred to as " germ resistance metal " in this article).According to the present invention, by in a vacuum the negative pole of target metal being ionized into the plasma body of particulate constituent, make the germ resistance metal deposition on matrix surface or among.The ion plasma deposition device, those (its content is incorporated in this for your guidance) described in International Patent Application Publication No. WO 03-044240 for example, can make amendment according to the present invention, and be used for implementing the controllability deposition of anti-bacterial material according to described method.
The factor of giving the film that utilizes disclosed technology and obtain with this superiority is to find new IPD technology to have produced the sedimentary increase of heavy ion (but not reduction) in fact it improved the quality of film.For many years for technicians, in the use of conventional cathode arc deposited technology, the most significant trend is to reduce oarse-grained deposition, so that produce cleaner and more uniform film.Understanding traditional in the industry is that macrobead is disadvantageous for the quality of deposit film usually.
By contrast, had been found that the increase of macrobead content has formed the effective way of the anti-microbial activity of controlled oxidation silver film.For silver is released into surrounding tissue rapidly, can adopt the thick oarse-grained pure AgO coating that do not contain fully.For further tuning release, utilized time-delay release embodiments (time-release scheme).
When utilizing cathode arc to be coated with to be deposited upon on the matrix, the corresponding amount of the macroparticle that may command ejects from target.Macroparticle is to eject and the metal droplets (blob) that is not gasified totally from target.These metal droplets are intensive, and are made up of pure target material.Usually, the surface of these metal droplets is charged, and most of materials then are electric neutrality.
When macroparticle when the plasma body, its outside surface is oxidized, has formed that a kind of particle outside has the AgO coating and the structure of inner " sugar of parcel " shape for fine silver.This just plays the capsular effect that similar time-delay discharges.
Because " shell " produced the effect that time-delay discharges in the shakiness setting of intrinsic AgO outer " shell " and the more stable fine silver.The silver suboxide exterior coating relatively promptly discharges its anti-microbial activity, has killed any bacterium in the peripheral region.In dispose procedure, inner fine silver is oxidized and discharge lentamente so that keep anti-microbial activity in for some time.The length of time is determined by the size of macroparticle.Therefore, can design the oarse-grained specific coating of specific dimensions, in the selected time period, to keep anti-microbial activity.Keep the length of active time as required, the size range of macroparticle is 10nm to 10 micron usually.
Wash-out is an important factor in anti-microbial activity; Yet the content of the silver that wash-out goes out is relevant with the anti-microbial activity of Ag/AgO coating unit.To anti-infective and formation microbial film, eluting rate must take place with certain level for effectively.Minimum eluting rate is about Ag of 0.005mg (0.0048mg/ square inch) per square inch.In at least 60 days, the anti-microbial activity of the silver suboxide coating by method presently disclosed preparation will be by this eluting rate wash-out.Silver/silver suboxide coating by the additive method preparation can be with constant rate wash-out above 7 days.
Another important feature of the present invention is the ability with silver suboxide coating flush mounting surface, therefore than the coating by other deposition, has obtained better adhesivity.Can control embedding technology by utilizing the electric arc control method at a distance of the specific distance of target,, can reach 10nm and darker embedding coating for metal and pottery so that obtain to reach 100nm and bigger for plastics.
The suitable device that is used to implement ion plasma deposition technology has been shown among Fig. 1.As shown in Figure 1, the negative electrode 1 with target material deposits in vacuum chamber 4.By by the energy 5 energy that provides that is applied on this negative electrode, on this negative electrode, make negative electrode 1 ionization by producing electric charge.By mobile matrix 2 near or select, control plasma components or make it point to matrix away from the controlling organization 3 of target 1.
Can also utilize the extra control of power supply 6 as shown in Figure 2, so that the control of article on plasma body component further to be provided by the control arc speed.
For example, be under the situation of silver at desired antibacterial metal, silver cathode and selected matrix are placed the vacuum chamber of ion plasma deposition device.Although also can use the silver metal of low-purity, the silver that is used as negative electrode is preferably medical grade silver (that is, purity is 99.99%), to avoid any potential toxicant.
Vacuum chamber is pumped to suitable operating pressure, and scope is 0.1mT to 30mT usually; Yet, the particular job pressure that IPD technology is effectively made the ability on the germ resistance surface with lasting release rate and do not relied on any common scope is 0.1mT to 30mT.Similarly, ion plasma deposition technology and do not rely on service temperature.Usually the scope of service temperature is 25 ℃ to 75 ℃, and the arbitrary temp in this scope all is applicable to makes the germ resistance surface.
Matrix can pass the deposition region with respect to (as on rotating disk) or the coiling that any direction of deposition material injection is rotated.Supply electric energy to produce electric arc to negative electrode at negative electrode.Be suitable under the voltage of source material, this electric energy is that scope is at several amperes of electric currents to the hundreds of ampere.Usually, voltage range is 12 volts to 60 volts, and the adjusting that suits of the size of corresponding source material, this size can be several inches to some feet.Electric arc with the silver metal cathodic electricity from being the plasma body of silver ions, electroneutral particle and electronics.Usually, oxygen is incorporated in the plasma body, and combines to form the silver suboxide particle with silver ions with the speed of 10sccm to 1000sccm.According to the required ion release rate and the end-use of matrix, the silver suboxide particle can have scope for from less than 1 nanometer to about 50 microns size of particles.
In order to obtain the effective release rate in one period time length, can also control the metal ion release rate on germ resistance surface.Be deposited on the matrix by composition, obtained this controlled metal and discharged the oxide compound (comprising unit price, two valency and multivalence oxide compound) of various structures.The combination of oxide compound presents different ion release rates, the control that its persistence to ionic concn and metal ion that has caused being used to improving anti-microbial activity discharges.Because they are oxidized in plasma body, the multivalence oxide compound can also form on the neutral metal particle.The composition of oxide compound that can be by forming various size and valence state has further strengthened the lasting release of deposition material.The benefit of this composition is the growth that ion discharges in the long time cycle.Silver oxide particle is deposited on matrix surface with the form of silver oxide particle dispersion then.
The validity of germ resistance surface in transmitting antibiotic response (anti-microbial) depends on the treatment time that is used to form this germ resistance surface.Formed germ resistance surface from 5 seconds to some minutes long treatment time with different antibiotic responses.
Also can be deposited on and obtain controlled metal release on the matrix by composition with different metal oxides.These compositions comprise silver and titanium, silver and gold and silver and copper, silver-bearing copper and gold.Other material can be used as a plurality of layers of codeposition metal, alloy or the alternative of conduct in various combinations and combination.The control of plasma environment and adaptability have allowed wider composition, and correspondingly, the customization coating of a wide region.
Further specify the present invention by following non-limiting examples.
Embodiment
Material and method
The silver-colored wash-out distribution of wash-out test with definite polypropylene sample that applies tested-carried out to the sample wash-out.Silver wash-out test provides a kind of quantivative approach that is used for determining in one period specified time cycle the content of the silver that discharges from test article.According to existing FDA laboratory practice rule (Good Laboratory Practice, GLP, Standards) 21CFR, the 58th part is implemented the present invention.Under the temperature of 37 ± 1 ℃ of temperature, each test article is extracted so that carry out silver-colored elution analysis by inductively coupled plasma spectrometry (ICP) from the USP 0.9%NaCl solution that is used for injecting.Respectively each sample is placed the USP 0.9%NaCl of 10mL to keep special time period.The used time period is 15min, 30min, 1hr, 2hr, 4hr, 8hr, 24hr, 2-7 days, 10 days, 15 days, 20 days, 25 days and 30 days in this research.On each time point, the liquid around the sample is moved in the clean Glass Containers, and fresh NaCl is added in the sample receiver.Make the liquid that shifts out reach the cumulative volume of 50mL with deionized water, carry out acid dipping (digeste) then and detect silver content by ICP.
Sample inhibition zone (ZOI) test-ZOI test is a kind of method that is easy to 24 hours test anti-microbial activities.This test is not quantitative, only can provide enough information to point out whether successive dilution test is allowed to.This test does not provide about tissue regeneration or downright bad information.
Sample serial dilution test-serial dilution test provide to unit to the accurate measurement of the number of bacteria of volume.When than control sample, it can provide the active quantitative measurment of antiseptic paint.
Bacterial solution by 0.5McFarland standard fabrication standard.With this standard calibration is that reading is between the 0.08OD to 0.1OD under 625nm, and the standard bacterial count that it obtains is 1.5 * 10
8Cfu/mL.
Though describe following embodiment of the present invention in detail, those skilled in the art to those embodiments modify with adjustment be conspicuous.Be to be understood that these modifications are included within protection scope of the present invention.
The conduit (disclosed method) that embodiment 1. silver medals apply
Identical step (procedure) preparation described in the embodiment 6 of utilization and U.S. Patent No. 5,454,886 applies (solver-coated) conduit of silver.Utilize magnetron sputtering that silver metal is deposited on the long a plurality of fragments of the 2.5cm of two-chamber latex balloon conduit.Come the implementation and operation condition based on disclosed embodiment as much as possible; That is, deposition is per minute 200A °; The argon operating air pressure is 30m Torr; The ratio of substrate temperature and coating metal silver point (T/Tm) is 0.30.In this embodiment and since matrix be the circle and be coarse, so input angle changes; That is, input angle changes along circumference, and the sidepiece and the top of crossing numerous surface elements in accurate scope.Antibacterial effect to streptococcus aureus (S.aureus), (table 1) have been tested by inhibition zone.
Table 1
| Patent 5,454,886 results reported | Experimental result | |
| Inhibition zone | 0.5mm | |
| T/Tm | 0.38 | |
| Inhibition zone | 16mm | <1mm |
| T/Tm | 0.30 | 0.30 |
With previous disclosed identical T/Tm condition under, and the identical condition of setting among the embodiment 6 of repetition and patent 5,454,889, the viewed inhibition zone (ZOI) that centers on pipe is significantly less than the ZOI that is reported.This ZOI test is as in patent 5,454, is reported among 886 the embodiment 1, utilizes streptococcus aureus (S.aureus) and carries out.
Embodiment 2.DC magnetron sputtering antimicrobial coating (disclosed method).
According to patent 5,454, the method for the embodiment 7 in 886.Under the following conditions: 0.5kW power, 40mTorr Ar/O
2, 20 degrees centigrade initial substrate temperature, the cathode/anode distance of 100mm, and the thickness of final film is 300nm, utilizes the DC magnetron sputtering to make that purity is that 99.99% silver is coated on the two-chamber latex balloon conduit that special teflon applies.Used working gas is commercially available Ar and 99/1 wt%Ar/O
2
Test the antibacterial effect that detects coating by inhibition zone.Acid hydrolyzed casein agar is dispersed in the Petri dish.Before inoculating with Staphylococcus aureus ATCC#25923 lawn, the surface of dry agar plate.(its indication through the producer is reconstructed for Disco, M.) preparation inoculum by Bactrol Discs.Simultaneously, after cultivating, the material of coating to be tested is placed agar surface.Under 37 ℃, culture dish is carried out hatching of 24hr.After hatching, measure ZOI, and according to following calculating of proofreading and correct inhibition zone: the diameter of proofreading and correct the test material of inhibition zone=inhibition zone-contact agar.Disclosed result illustrates, and does not have inhibition zone for uncoated sample.For the operating air pressure at 40mTorr, 99/1wt%Ar/O
2The conduit of middle sputter has been reported the gauged inhibition zone with 11mm.
In table 2, listed and under open condition, repeated to implement experiment.Observe little ZOI less than 1mm.
Table 2
In repeating above-mentioned open condition, experimental result shows the little ZOI less than 1mm.
As patent 5,454, found among 886 the embodiment 11 that present embodiment has shown the situation of the art processes that is used to prepare the composite antibiosis coating that forms by reactive sputtering.Table 3 has been listed used condition in disclosed sputtering condition and the comparative study (than by the experimental result that step obtained in the following discloses method).
Table 3
| The disclosed test of sputtering condition |
| Target 99.99% Ag 99.99% |
| Working gas 80/20% Ar/O 2 80/20％ ArO 2 |
| Operating air pressure 2.5-50mTorr 40mTorr |
| Power supply 0.1-2.5kW 0.5kW |
| Substrate temperature-5 is ℃ to 20 ℃ 20 ℃ |
| Anode/cathode is apart from 40mm to 100mm 100mm |
| Bottom air pressure (base P)＜4 * 10 4Torr <4×10 4Torr |
| ZOI 6mm-12mm 0mm-2mm |
Present embodiment has shown the validity of antiseptic paint in gram-positive and Grain-negative organism scope.The organism that is used for the test of general inhibition zone is: gram-positive bacteria enterococcus faecalis (E.faecalis), streptococcus aureus (S.aureus MR), and S.epidermis.Gram-negative bacteria is intestinal bacteria (E.coli), Klebsiella Pneumoniae (K pneumoniae) and P.aerugosia.
Carry out the used method of ZOI test and be (maximum) step by step tray of 4 days transfer at most.Each bacterium is tiled on the pancreatin soy agar.With ready-formed plate inoculated bacteria, be divided into three equal parts, and after cultivating, the one inch long foley's catheter sample that is coated with the 200nm silver suboxide placed the center of each part.Under 37 ℃, sample is placed incubator, measured ZOI at 24 hours, 48 hours, 72 hours and 96 hours.
Total ZOI is defined as the width that ZOI deducts sample.Experiment has been carried out the measurement of total ZOI, and it has been divided into two parts hereto.If do not have the ZOI that can survey and do not have microbial film, and organism not growth cross or be connected to sample, be 0.0mm then with survey record.When observing microbial film, it is recorded as 1.0mm.The repetition step by step tray shifts, until having recorded microbial film or having shifted the observed value that records 0.0mm for 2 times.Each organism has three plates, has three data points for side by side sample and each plate of contrast conduit.All measure every day.The mean value of three observed values of getting each plate is to obtain the plate ZOI of every day.Doing these is in order to compensate the impact (swipe) that concentration is overweight or kick the beam.The observed value of all records is all in mm.0.0 observed value shows biology growing at silver-colored sample, but does not adhere to or produce microbial film on silver-colored sample conduit.All control samples all had microbial film without any exception from the 1st day.The result is shown in the table 4.
Table 4
First day
Present embodiment shows the rabbit body build-in test of two sections identical tube materials with 200nm silver suboxide coating.Test set is the ETO-sterilization.For in two sections conduits each, make four conduit germ resistance part fragments (length is about 4 inches).Use this test set and maintenance at room temperature.
Eight conduit fragments (four fragments of each tube material) are implanted in the female New Zealand white rabbits altogether.Before implanting the 1st day, weigh and his the life/xylazine cocktail (87mg/mL restrains his and orders, the 13mg/mL xylazine) of gram of intravenous injection 0.1mL/kg is anaesthetized.Animal is that 23-25 week is big, and is weighed as 2.63kg at the 1st day.
Week after conduit is implanted, (aggressiveness, challenge) organism (streptococcus aureus or intestinal bacteria) places on the skin around each conduit entry site (two fragments of each tube material be subjected to infection of staphylococcus aureus and remaining two fragments of each tube material are subjected to coli-infection) with infectivity.Put to death animal at infectation of bacteria after 48 hours.
The parameter of handling is described in the following Table 5.According to the scheme of being taked, infectation of bacteria occurs in the 8th day.
Table 5
The other district of vertebra utilizes electric clipper to prune, and utilizes the ethanol of povidone iodine and 70% to prepare.Animal has eight implantation positions along its back.Each position is apart from center line 2.5cm-5.0cm, and the position is at a distance of about 2.5cm.Implantation position utilizes permanent marks to identify.
At each implantation site, enter into muscle with No. 16 needle-penetration skins.ID along pin pierces in the muscle with the conduit fragment, and pin is removed, make conduit segmental half enter muscle by skin and implanted.A part at each site implantation catheter material.With each four fragments in identical two sections, eight implants are implanted rabbits altogether.The conduit fragment that exposes is covered with aseptic dressing.Determined the position of the implantation site on back part of animal in the table 6.
Table 6
At the 8th day, the conduit fragment of aseptic dressing from each exposure removed.Skin around each conduit in-position is accepted 1mL and is comprised 2.2 * 10
5CFU/mL streptococcus aureus and 5.10 * 10
2Instil in the surface of the colibacillary suspension of CFU/mL.With a fragment in each tube material of infection of staphylococcus aureus, with a fragment in each tube material of coli-infection.After inoculation, cover the conduit fragment again with aseptic dressing.Listed the organism of the inoculation of each site use in the table 7.
Table 7
| Location number | Side | The zone | The material of implanting | The organism of inoculation | Note |
| 1 | A left side | Head | 3659-16 | Streptococcus aureus | Usually give the 1mL bacterial suspension |
| 2 | A left side | The head middle part | 3659-16 | N/A 1 | N/A |
| 3 | A left side | The head middle part | 3659-17 | N/A 1 | N/A |
| 4 | A left side | The vertebra tail end | 3659-17 | N/A 1 | N/ |
| 5 | Right | Head | 3659-16 | N/A 1 | N/A |
| 6 | Right | The head middle part | 3659-16 | Intestinal bacteria | Give the 1mL bacterial suspension partly |
| 7 | Right | Vertebra tail end middle part | 3659-17 | Intestinal bacteria | Give the 1mL bacterial suspension partly |
| 8 | Right | The vertebra tail end | 3659-17 | Streptococcus aureus | Give the 1mL bacterial suspension partly |
N/A=does not apply
At the 10th day, according to brain chemistry optimum procedure agreement (Brain ChemistryOptimization Program protocol) 01-11-21-22-02-026, the euthanasia solution that intravenous injection is purchased made animal euthanasia.Whole implant is carried out aseptic collection, and carry out quantitative bacteria-measuring.Conduit region at muscle and skin is marked with surperficial label.Because it is sightless that a plurality of conduits have been retracted and have implanted pipeline, so do not collect label in this research.Place the formalin of 10% neutral buffered with implanting vestige muscle parts on every side, and (Fort Collins CO), is estimated by the animal doctor's pathology expert who is well received by the public to submit to Colorado Histo-Prep.For 4 in 8 implantation sites (1,6,7, reach No. 8 sites), respectively the inside and the external portion of implant are collected in the tryptic soy broth (Tryptic Soy Broth).These are the sites that still have a part that is in the conduit outside the skin.
Clinical observation illustrates rabbit and kept health, and the sign of not shown infection, and is as shown in table 8.
The clinical observation of table 8 rabbit health
Explain:
It is normal that G0=seems; Cleverness, vigilance also are swift in response
S0=ight soil is normal
S1=ight soil soft (soft)
A0=consumes the food of normal amount
For each test material, an implantation site inoculation streptococcus aureus, implantation site inoculation intestinal bacteria are cultivated (the 1st, 6,7, reach No. 8 sites).For the site of inoculation, the position that is designated inside and outside two implants has been carried out the evaluation of microorganism growth and identification.The above duct portion of skin is designated outside implantation site, and the following duct portion of skin is designated inner implantation site.
For remaining four implantation sites (2-5 position), do not implement inoculation, inoculating the same day (the 8th day) simultaneously, there is not the visible implant in the skin outside.For these sites, the subcutaneous part of conduit is carried out evaluation about microbial growth and identification.
For implanting with the 3659-16 tube material and, discerning the just growth (positive growth) of infection biological body at inner and outside implantation site with the site (No. 1 site) that streptococcus aureus infects.For implanting with the 3659-16 tube material and, having the bacterial growth that is identified as Staphylococcushominis at inner implantation site with the position (No. 6 position) that intestinal bacteria infect; This growth is owing to environmental pollution.In this site, do not recognize the growth of infectious organisms (intestinal bacteria) at inner or outside implantation site.
For the site (No. 8 position) of implanting with the 3659-17 tube material and infecting with streptococcus aureus, only implantation site recognizes the positive growth of infection biological body outside.For implanting with the 3659-17 tube material and, not having growth at inner or outside implantation site with the site (No. 7 site) that intestinal bacteria infect.
For remaining four nonvaccinated implantation sites (2-5 position), there is not bacterial growth.See Table 9.
Table 9
Microorganism growth result from implantation position
N/A=can not apply
The obvious visible evidence that does not all have tissue reaction or infection at any implantation site.For all implantation sites, in the subcutaneous fascia and the black variable color of muscle existence of implantation position to ash.The result summarizes in table 10.
Table 10
Corpse detects to be observed
Corpse detects to be observed
Treated animal is implanted implantation position condition normal observation
2
Number position material
Reaction of conduit inorganization or infection that A 17 1 3659-16 pull out from muscle
Obvious visible evidence
Duct portion in the 2 3659-16 muscle is received inorganization reaction or infection
Return the obvious visible evidence of half (back out halfway)
Reaction of duct portion inorganization or infection in the 3 3659-17 muscle
Obvious visible evidence
4 3659-17 are reaction of the duct portion inorganization in muscle or infection still
Obvious visible evidence
5 3659-16 are reaction of the duct portion inorganization in muscle or infection still
Obvious visible evidence
Reaction of conduit inorganization or infection that 6 3659-16 pull out from muscle
Obvious visible evidence
Reaction of conduit inorganization or infection that 7 3659-17 pull out from muscle
Obvious visible evidence
Reaction of conduit inorganization or infection that 8 3659-17 pull out from muscle
Obvious visible evidence
N/A=does not apply
The result shows the anti-microbial catheter that has flooded silver/silver suboxide and has avoided bacterium, bacterium colony, reached biomembranous formation.The antibiotic effect of all implantation sites all is consistent, even also remaining effective with the 8th day antiseptic paint behind intestinal bacteria or the streptococcus aureus infectation of bacteria.Do not observe necrosis.Pathology is consistent with the foreign body reaction in the muscle, and has inflammatory reaction more violent in subcutis.
The wash-out of embodiment 6 silver suboxide coatings
20 samples altogether are to the 1cm that applies with typical silver suboxide coating
2Polypropylene estimate.All choose two samples in ten different samples from two experimental group.Utilize inductively coupled plasma to carry out this test twice, with the content of the silver determining on each time point, to exist.For each test group, ten total values that obtain are obtained mean value then.The wash-out value illustrates by the mg/ sample, and in this case, it is the mg/ square inch.
In first 24 hours, all samples all present consistent behavior in NaCl solution.Reaching steadily near the time point at 24 hours in these values, (leveled off) occurred a small peak at four hours near the time point before.
All samples all have very consistent behavior.From the 1st day to the 5th day, these values were all quite stable; Near the 6th day time point, peak value occurs then, then reached steady from the 7th day to the 30th day.
At all time points, be about 0.005mg (0.0048mg/ square inch) per square inch for the average wash-out value of the polypropylene sample that applies.In the whole process of this research, in physiological saline, utilize wash-out value and total silver number of about 1.05mg (obtaining) per square inch for the polypropylene sample, show quite consistent silver-colored wash-out, at 4 hours time points and the small peak value of discovery after 6 days by external testing.
Healing test in the body of embodiment 7 ePTFE coated substrates
By the body build-in test, present embodiment has shown that 200nm silver suboxide coating can not cause necrosis.Utilize the 200nm silver suboxide coating coating 1cm of standard
2The ePTFE sample, and according to generalized, in its subcutaneous implantation rabbit with 6 of the foregoing descriptions.Shifted out matrix at the 9th day and the 22nd day, with the healing of the tissue of research around the silver suboxide coating part of implanting.The result summarizes in table 11.
Table 11-is for the historic records of 200nm silver suboxide
| Treatment group | Implantation is held time, fate | EPTFE//visceral surface | EPTFE//reticulation surface | Silver particles/particle is observed |
| The uncoated net dress of |
9 | One to several mps layers; Sscs 10+ layer with ncf | MF: the mps that is had occ gcs and have a ncf reticulation centers on: filled by the mps with ncf; Occ pmns﹠amp; Baso | Do not have |
| 22 | The suitable little fibrosis of being made up of inoblast (spindle cell) in the collagen parent responds.Scavenger cell at the interface and occ giant cells | In the fibrosis response on ePTFE surface and the fibrosis that the continues response in the reticulation, and around the monofilament composition | Do not have | |
| Reticulation sample 1 200nm that silver suboxide applies | 9 | One to several big mps layers.Losing of fibrosis lamination prompting nuclear.Nucleosis.Tangible gcs. | The Dec no reticulation of MF:mps: sparse cell scleroproein reticulation.Fragment of tissue.The focal zone of downright bad fragment | Obvious gcs with the bigger silver-colored particulate part of occ, successive have the thin layer of the mps on part-visible (vis) surface. |
| 22 | Observe representational fibrosis response.In being arranged, the scavenger cell of response observes black ppt (matching) with the refrangible fragment.At the interface have a mps ﹠amp; The refrangible fragment of gcs | Fibrosis response on the TFE surface.A large amount of baso/ mastocyte in the response.Observe the black ppt (refrangible fragment) of occ.At the interface have a mps ﹠amp; The refrangible fragment of gcs | In fibrosis response and TFE interface, observe and reflect that fragment matches has mps ﹠amp; The black ppt of gcs. |
| Silver suboxide applies net dress thing sample 2 |
9 | One mps to several layers appropriateness ncf | MF: adorn thing by the net that the mps with occ gcs centers on // reduces slightly: appropriate ncf has mps; Significantly vascular response | Freq Ag particle with mps.Fibrosis thin layer (visible surface) in most of cell-the have part of mps |
| 22 | Observe representational fibrosis response.Dispersive has the mps (refrangible fragment) of black ppt and has the thin layer of the mps that comprises black ppt.The TFE surface of aligning by mps wo fragment | Fibrosis response on the TFE surface.The Occ dispersive has the mps of black ppt | Dispersive ppt with reticulation response and internal organ response with mps |
Abbreviation used in the table 11 is as follows:
The Occ chance
The PMSs polymorphonuclear cell
The Mps mucopolysaccharide
The SSCs fusiform cells
The MF ultra-fine fibre
The Baso basophilic granulocyte
The Ncf neutrophilic chemotactic factor
Embodiment 8-has the cathodic arc deposition of removable matrix
Present embodiment has shown removable matrix is how to influence the macrobead size, thereby the release of controlled oxidation silver.
Matrix (matrix one) placed with target have on the removable supporter of 30 inches distances.With the indoor level that is pumped to 5E-4 Torr.Electric current starting arc with 100amps and 16 volts.Oxygen is introduced in the chamber with the speed of 200 SCCM.Make matrix more near target with per 15 seconds one inch speed.Continue to carry out, until matrix and target at a distance of 8 inches.
In comparative embodiment, under identical electric current, voltage, total time and oxygen gas flow rate, matrix (matrix two) is placed distance at a distance of 30 inches of targets.This time, matrix keeps static.
Initial ZOI test is illustrated in the circle that has same size in 24 hour time period.Implement plate at some bacteriums and shift, the result is shown in the table 12.Can find out that the matrix that is moved toward target in depositing operation is compared and kept the immobilized matrix to show anti-microbial activity in the longer time period.
Except that the ZOI test, also utilize the sem analysis method to detect the cross section of two matrixes.In sample one, oarse-grained quantity and size increase along with the thickness of film; That is, have still less and littler macrobead near matrix, and number and size increase along with the growth of film thickness.On the contrary, the cross section in the sample two has macrobead seldom and is uniform.
Table 12
First day
The control of embodiment 9-electric arc
Present embodiment illustrated the electric arc controller how with the oarse-grained size and the frequency dependence that are produced.In this embodiment, make two samples move.At first, sample three does not have the electric arc controller, and matrix is placed distance at a distance of 12 inches of targets.The second, sample four has the electric arc controller, and also matrix is placed the distance at a distance of 12 inches of targets.Two samples all are positioned in the chamber, different number of times are implemented in different operations, and be pumped to 5E-4Torr.According to beginning to be provided with electric arc with 100Amps for all electricity supplies.Each target has two sources of supply to obtain the initial total amount of 200amps.Sample three moves five minutes under the situation that does not have the electric arc controller.Sample four moves under preferred 300 hertz of current conversion speed.
Conversion on the target always remains on 200amps, changes (ramped up and down) but height all can appear in each power supply, so at any time, the electric current on source of supply is also unequal.This moves specific distance with regard to forcing electric arc in the specific time, thereby controls oarse-grained density and size.
On sample three and four, implement the SEM cross-sectional analysis.Can be observed, be that the sample three of comparing, sample four have the bigger macrobead size and the mean value of density uniformly although film runs through its whole thickness.Macrobead mean sizes in the sample three is about one micron, and density is 10
3/ cm
2Macrobead mean sizes in the sample four is about three microns, and density is 10
4/ cm
2
The vitro test of the silver suboxide on the embodiment 10-metal
Present embodiment has shown the validity of the AgO coating on Ti-6-4 and CoCrMo.Utilize common method washed samples five and six, and be placed in the vacuum chamber and with the distance of target at a distance of 12 inches.Typical silver suboxide is coated with is deposited upon on the sheet, and carry out the ZOI test with three days time.Sample five is Ti-6-4, and sample six is CoCrMo.The result sums up in table 13.
Table 13
First day
Although the present invention is described with reference to its specific embodiment; those skilled in the art should be understood that; under the situation of true spirit of the present invention and protection domain; can make various variations and modification, and be equal to substitute mode, especially; what it is also understood that is; under the situation that does not deviate from protection scope of the present invention, chemistry and pharmacy details in each design can have nuance, or revise by the those of ordinary skill of this area.All such modifications all should be within the scope of appending claims.
Claims (26)
1. cathode arc ion plasma deposition method that is used to prepare the antiseptic paint on matrix comprises:
Selected matrix is positioned between anode and the negative electrode target, and described target comprises ionizable metal;
The oxygen introducing is held in the vacuum chamber of described negative electrode target and described matrix, wherein, described chamber is pressurized to about 0.1mTorr to about 30mTorr;
Between described anode and described negative electrode target, produce arc-over, wherein, be fed to electric energy on the described electric arc alternatively by variable control, so that the preparation scope is at the particle of 1nm to 50 μ m; And
In arc discharge process, in a scheduled time under the temperature between about 25 ℃ to about 75 ℃, about 1 inch adjust to about 50 inches scope described matrix near or away from the motion of described target, with the thickness that has in deposition on the described matrix at about 50nm high-density, adhesivity antiseptic paint in about 5 mu m ranges extremely.
2. method according to claim 1, wherein, the described electric energy that is fed on the electric arc carries out external control by independent variable power supply or by at least two independently variable power supplies that are connected to described negative electrode target with opposite location.
3. method according to claim 2 wherein, in the process of deposition 100-200nm coating, is adjusted to about 12 volts extremely about 60 volts so that the electric current between 5 amperes to about 500 amperes to be provided with the described electric energy that is fed on the electric arc on described matrix.
4. method according to claim 1, wherein, described ionizable metal is the metal that is selected from the group of being made up of silver, gold, platinum, copper, tantalum, titanium, zirconium, hafnium and zinc.
5. method according to claim 4, wherein, described metal is a silver.
6. method according to claim 1, wherein, described matrix comprises metal.
7. method according to claim 6, wherein, described matrix is selected from by titanium, steel, chromium, zirconium, nickel, their alloy and the group formed of their combination.
8. method according to claim 1, wherein, described matrix comprises polymkeric substance or pottery.
9. method according to claim 8, wherein, described polymkeric substance is polypropylene, urethane, EPTFE, PTFE, polyimide, polyester, PEEK, UHMWPE or nylon or their combination.
10. method according to claim 9, wherein, described polymkeric substance is PEEK or polyethylene.
11. a high-adhesiveness Ag/AgO germ resistance film that is deposited on the metallic matrix, wherein, described Ag/AgO infiltrates the degree of depth that described matrix reaches about 10 nanometers.
12. a high-adhesiveness Ag/AgO germ resistance film that is deposited on the polymeric matrix, wherein, described Ag/AgO infiltrates the degree of depth that described surface reaches about 100 nanometers.
13. Ag/AgO germ resistance film according to claim 11, it deposits to and is selected from by in titanium, steel, chromium, zirconium, nickel, their combination and the metal of the group of alloy composition.
14. Ag/AgO germ resistance film according to claim 12, it deposits on the polymeric matrix that comprises the polymkeric substance that is selected from the group of being made up of polypropylene, urethane, EPTFE, PTFE, polyimide, polyester, PEEK, UHMWPE or nylon and their combination.
15. matrix according to claim 1, it comprises the device that is selected from the group of being made up of conduit, lobe, support and implant.
16. matrix according to claim 15, wherein, described device is a conduit.
17. matrix according to claim 15, wherein, described conduit, lobe, support and implant comprise polymkeric substance, metal, pottery or their combination.
18. matrix according to claim 16, wherein, described conduit comprises polymkeric substance.
19. matrix according to claim 18, wherein, described polymkeric substance is selected from by polypropylene, urethane, EPTFE, PTFE, polyimide, polyester, PEEK, UHMWPE, reaches the group that nylon is formed.
20. cathode arc ion plasma deposition method that is used for improving the anti-microbial activity of silver/silver suboxide ion plasma deposition film, comprise the distance of adjusting between matrix and the cathode arc target, and the monitoring quantity that deposits to silver in described film relevant with the distance of described matrix and described target, wherein, the reduction of the silver/silver suboxide ratio in the anti-microbial activity of the raising of described film and the described film is associated.
21. method according to claim 20 further comprises the particle size of adjusting arc speed and monitoring sedimentary silver/silver suboxide, wherein, the increase of macrobead number has improved the anti-microbial activity of described film.
22. coating by method preparation according to claim 21.
23., further comprise increasing depositing time to obtain required film thickness according to claim 20 or 21 described methods.
24. silver/silver suboxide germ resistance film that is deposited on metal, polymkeric substance or the ceramic surface, wherein, described silver/silver suboxide is embedded into described metallic surface reaches the degree of depth of about 10nm to about 10nm, described film has the thickness between about 5 μ m at about 50nm, and it can be after use reaches at least in time of 28 days and keep anti-microbial activity.
25. silver according to claim 24/silver suboxide germ resistance film, it deposits on the surface of metal, polymkeric substance or ceramic medical treatment device.
26. film according to claim 25, wherein, described medical treatment device is conduit, support, implant or lobe.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76276906P | 2006-01-27 | 2006-01-27 | |
| US60/762,769 | 2006-01-27 | ||
| US60/763,262 | 2006-01-30 | ||
| US60/776,537 | 2006-02-25 | ||
| US60/779,917 | 2006-03-06 |
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| Publication Number | Publication Date |
|---|---|
| CN101437977A true CN101437977A (en) | 2009-05-20 |
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101991876A (en) * | 2009-08-14 | 2011-03-30 | 机械科学研究总院先进制造技术研究中心 | Manufacture method of prosthesis with self-antibacterial action |
| TWI499683B (en) * | 2011-11-21 | 2015-09-11 | Ever Brite Technology Products Inc | A method of forming an antibacterial film on the surface of an object by means of a cathodic arc method and a magnetron sputtering method |
| CN105343938A (en) * | 2011-09-30 | 2016-02-24 | 先健科技(深圳)有限公司 | Medical instrument |
| CN111744752A (en) * | 2020-05-27 | 2020-10-09 | 河北复朗施纳米科技有限公司 | Technological method for spraying antibacterial wear-resistant material on surface of intelligent lock |
| CN113636870A (en) * | 2021-07-13 | 2021-11-12 | 广东富强陶瓷有限公司 | Production process of antibacterial wear-resistant anti-skid glazed ceramic tile |
| CN116180492A (en) * | 2023-03-06 | 2023-05-30 | 江苏卫星新材料股份有限公司 | Silver ion antibacterial paper and preparation method thereof |
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2007
- 2007-01-19 ES ES07762413T patent/ES2361443T3/en active Active
- 2007-01-19 CN CNA2007800103843A patent/CN101437977A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101991876A (en) * | 2009-08-14 | 2011-03-30 | 机械科学研究总院先进制造技术研究中心 | Manufacture method of prosthesis with self-antibacterial action |
| CN105343938A (en) * | 2011-09-30 | 2016-02-24 | 先健科技(深圳)有限公司 | Medical instrument |
| TWI499683B (en) * | 2011-11-21 | 2015-09-11 | Ever Brite Technology Products Inc | A method of forming an antibacterial film on the surface of an object by means of a cathodic arc method and a magnetron sputtering method |
| CN111744752A (en) * | 2020-05-27 | 2020-10-09 | 河北复朗施纳米科技有限公司 | Technological method for spraying antibacterial wear-resistant material on surface of intelligent lock |
| CN113636870A (en) * | 2021-07-13 | 2021-11-12 | 广东富强陶瓷有限公司 | Production process of antibacterial wear-resistant anti-skid glazed ceramic tile |
| CN116180492A (en) * | 2023-03-06 | 2023-05-30 | 江苏卫星新材料股份有限公司 | Silver ion antibacterial paper and preparation method thereof |
| CN116180492B (en) * | 2023-03-06 | 2024-02-23 | 江苏卫星新材料股份有限公司 | Silver ion antibacterial paper and preparation method thereof |
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| ES2361443T3 (en) | 2011-06-17 |
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