The coating process of medical function coating and applicationTechnical field
The present invention relates to a kind of technology of field of functional materials, the coating process of specifically a kind of medical function coatingAnd application.
Background technique
Well-known to those skilled in the art, there are substrate applications window narrows, coating are solid for conventional medical functional coating technologyA series of disadvantages such as change means are single, curing rate is slow, coating fastness and poor durability.For example, medical intervention is led on the marketThe adaptability problem of the hydrophilic generally existing inert base of superslide coating on pipe.For by silicon rubber substrate, even across superThe various surface treatments such as sound cleaning, plasma, silane coupling agent, hydrophilic coating are also easy to that " delamination " phenomenon occurs.Example againSuch as, many medical antibacterial products are all to achieve the purpose that sterilization, therefore Durability of antimicrobial effect and stabilization by release antibacterial materialProperty is poor.For another example, what the anti-fog coating of endoscope lens was more satisfactory at present can only maintain anti-fog effect 3 months, coatingWater resistance acid resistance is poor, can gradually decrease in vivo and loses anti-fog effect using easily leading to coating surface.For performing the operationAnti-stick coating on electric knife, ultrasound knife, tradition coating be all teflon coatings, and the processing performance of teflon material itself compared withDifference, processing conditions harshness are well known.
Existing research shows to use medical inert material, such as stainless steel, polypropylene, silicon rubber, polytetrafluoroethylene (PTFE)Plasma surface treatment can bring many active influences.But the timeliness phenomenon of plasma surface treatment is abilityIt is in domain well known to technical staff, i.e., plasma treated, new radical amount that most substrate surfaces obtain andSurface can all can occur obviously to decay within a short period of time, or even return to untreated state, this time short then a few minutes,Long then a couple of days, and this is in the more demanding GMP of product control (Good Manufacturing Practice, pharmaceutical production quality pipeReason specification) it is flagrant in grade product manufacturing.
Summary of the invention
The present invention In view of the above shortcomings of the prior art, proposes a kind of coating process of medical function coating and answersWith, functional coating have easily solidification, without choice of the substrates, with substrate caking power is strong, coating it is fine and close it is transparent, cured product is nontoxic,The advantages that coating is durable, the shortcomings that overcoming conventional medical functional coating.
The present invention is achieved by the following technical solutions:
The present invention relates to a kind of coating process of medical function coating, comprising:
Surface preparation；In two steps, successively using the mixed gas for including fluorocarbon gas and inorganic oxygen-containing gas including containThe mixed gas of hydrocarbon-based gas and inorganic oxygen-containing gas carries out plasma surface pretreatment to medical material；
Post-processing；The coating functions polysilazane solution on through the pretreated medical material of plasma surface, and it is solidChange forms medical function coating.
Plasma surface pretreatment in the present invention includes plasma activated chemical vapour deposition and plasma etching twoKind situation, plasma activated chemical vapour deposition and plasma etching are existed simultaneously and are vied each other, however, plasmarizedIt learns vapor deposition and wants much lower compared to energy of plasma used in plasma etching.
The fluorocarbon gas that the plasma surface pretreatment uses is the total number of carbon atoms 1~6, and at least contains oneAny one in the organic gas of a perfluoro alkane base or perfluor alkylene alkyl, structural formula are as follows:
Wherein, m, n are the integer more than or equal to 0, R1,R2, R3 are any organic group or hydrogen.
In some technical solutions, the fluorocarbon gas is carbon tetrafluoride, perfluoroethane, hexafluoropropane, heptafluoro-propane, eightAt least one of fluorine-containing alkane such as fluoro-propane, perfluorinated butane, perflenapent, Decafluoropentane, perflexane.
In some technical solutions, the fluorocarbon gas is trifluoroethanol, trifluoroacetone, five fluorine propionic acid, five fluorine valeric acids, sixFluorine isopropanol, octafluoropentanol, octafluoro pentane -2,3- diketone, hexafluoro pentane diol, hexafluoro isopropyl methyl ether, acrylic hexafluoroThe fluorine-containing alcohols such as isopropyl ether, contain at least one of carboxylic acid fluoride, fluorine-containing ether at fluorinated ketones contained.
The inorganic oxygen-containing gas that the plasma surface pretreatment uses is water, hydrogen peroxide, ozone, oxygen, dioxyChange at least one of carbon, nitrogen dioxide, nitric oxide；In surface preparation, inorganic oxygen-containing gas is in two kinds of mixed gasIn ingredient determined according to substrate, can be consistent, be also possible to variation.
Plasma surface pretreatment use containing hydrocarbon-based gas be straight-chain hydrocarbons, epoxy hydrocarbon, aromatic hydrocarbons, alcohol, carboxylic acid,At least one of ether, furans, organic amine；It more preferably, is straight-chain hydrocarbons, epoxy hydrocarbon, alcohol, any one or two kinds in ether.
The straight-chain hydrocarbons is at least one of alkane, alkene, alkynes, it is therefore preferable to the alkane, alkene of the total number of carbon atoms 1~4Hydrocarbon, alkynes.
The epoxy hydrocarbon preferably epoxy hydrocarbon with side chain.
The alcohol is monohydric alcohol or polyalcohol, preferably dihydric alcohol.
The ether is unitary ether or polynary ether, preferably binary ether.
Mixed gas further includes the complementary gas for increasing surface treatment effect, institute in the plasma surface pretreatmentStating complementary gas includes at least one of hydrogen, nitrogen, argon gas, helium, ammonia.
In addition to gas system, involved running parameter does not do specific limit in plasma surface treatment process of the present inventionIt is fixed, such as gas mixture ratio, gas flow, radio frequency discharge power, discharge time, working vacuum degree, as long as meeting institute of the present inventionThe gas system feature stated, it should all be included in defined in the present invention and within the context of equivalent.
The functional polyalkylene silazane solution includes coating substrate, and the coating substrate includes inorganic polysilazane, organicAt least one of polysilazane, modified inorganic polysilazane and modified organopolysilazane；
Preferably, the coating substrate include with inorganic polysilazane, organopolysilazane is mixed and modified and/or grafting changesThe functional material of property；
Preferably, the coating substrate includes mixed and modified with modified inorganic polysilazane, modified organopolysilazaneFunctional material.
Polysilazane material generally includes inorganic polysilazane and organopolysilazane, the former is also known as the poly- silicon nitrogen of perhydroAlkane is free of C element organic group in addition to Si, N and H element, and the difference of the latter is the H on the Si -- H bond of part by the alkyl containing CReplace, common are methyl, ethyl, vinyl, fluorine-containing alkyl.
Polysilazane contains special Si-N key, Si -- H bond and N-H key, they can be with hydroxyl, carboxylic in addition at normal temperatureOutside the chemical reaction that base, amino occur, it can also occur instead with containing organic matters such as alkenyl, isocyanate group under catalysts conditionsIt answers, such as under the effect of Karst catalyst, chloroplatinic acid or other platinum catalysts and the generation Si―H addition reaction of organic matter containing alkenyl is anti-It answers, realizes and be modified, obtain modified inorganic polysilazane, modified organopolysilazane.
Although the present invention is not also particularly limited the method for modifying of above-mentioned modified inorganic or organopolysilazane, showAnd be clear to, occurred by inorganic or organopolysilazane and the hydroxyl of modified material, carboxyl, amino, alkenyl, isocyanate groupChemical reaction be preferably select, meanwhile, also should include the modification material not chemically reacted with polysilazane material with otherMaterial carries out that physical mixed is modified, the polyethylene glycol that blocks such as thermoplastic acrylic resin, bi-methoxy, anhydrous quaternary ammonium salt, organicIt is mixed and modified between silicon, calcium carbonate, silica and titanium dioxide filler etc. and polysilazane material.In addition to this, this hairWithin the scope of modification polysilazane that is bright unmentioned or being obtained by other methods should also be included in defined in the present invention.
The coating uses at least one of dip-coating, spraying, spin coating, brushing, roller coating mode；Preferably, using dip-coating, sprayIt applies, combination any one or two kinds of in spin coating；More preferably, dip-coating 1-3 times or spin coating 1-3 times or dip-coating and spin coating collocation coating 1-3 times.
The solidification includes normal temperature cure, humidity cure, hot setting, high temperature and heavy wet solidification, ammonia solidification, UV lightAt least one of change, infrared photocuring；It is preferred that at least one of normal temperature cure, humidity cure, ultraviolet light solidification.
It is known in the art that the curing mode of polysilazane coating is more flexible.It at low concentrations can be with single application shapeIt at nano-scale coating, can also repeatedly coat to form sub-micron-micron order coating, can also be formed by the single application of high concentration micro-Meter level coating.It, can also be by under hot setting, annealing, room temperature or damp condition in addition to the solidification of above-mentioned one or more modesThe different post-processing combinations such as resolidification realize solidification, or even can also complete further modification by the modes such as ultraviolet, infraredAnd solidification, to reach the purpose for obtaining different surface propertys after hardening.The variation of these technologies should all be included in the present inventionWithin defined and equivalent context.
The present invention relates to a kind of medical material, the surface cure of the medical material has medical function coating, described medicalFunctional coating is made of above-mentioned coating process.
The medical function coating includes but is not limited to following coating form: hydrophilic coating, superslide coating, lower resistance applyLayer, antimicrobial coating, anticoagulant coatings, anti-fog coating, anti-stick coating, nonpolluting coating, wear-resistant coating, waterproof coating, choke coating.Above-mentioned medical function coating may be simple function, it is also possible to and it is multifunctional unit, such as hydrophilic superslide coating, hydrophilic anti-Bacterium coating, wear-resisting waterproof coating, antifog anti-stick coating, waterproof choke coating.It is emphasized that the technology through the inventionThe object of the medical function coating that means obtain, practical application and implementation should not be unduly limited in medical field, such as anti-Bacterium coating and nonpolluting coating can also be used as common household application, also can be used in addition to being used for all kinds of medical instruments and medical materialIn public capital construction facility, etc..
Technical effect
Compared with prior art, the present invention has the following technical effect that
1) present invention in be carried out in two steps plasma surface pretreatment be most of substrates, including inorganic, metal andPolymer base material, provide an active group density it is certain and be uniformly distributed, surface can decay unconspicuous surface；On the one handKeep adaptability, the compatibility of substrate and polysilazane coating more preferable, enhances the chemical bonding of polysilazane coating material and substratePower, can make subsequent obtained polysilazane coating layer thickness is controllable, be more evenly distributed, adhere to it is stronger；On the other hand, relative to paintingThe time that Surface Treatment with Plasma needs for dress is extremely short, and the processing of industrialized mass production plasma is likely to production capacity occurSuperfluous situation, the plasma surface treatment timeliness being carried out in two steps based on the present invention is long, can be avoided in this casePlasma-treated surface because cannot process failure and energy waste caused by coating in time, make production operating moreFlexibly；
2) coating and quick solidifying；Polysilazane material can form micron-sized dense coating by dip-coating in tens seconds,Normal temperature cure can be completed in dozens of minutes to several hours；
3) high biological safety；It is formed after polysilazane material solidification with SiOxBased on inorganic network or it is inorganic-haveMachine hybridization network structure is similar to glass and ceramics, safe and non-toxic；
4) coating durability is good；Pencil hardness can be resistant to water, acid, salt up to 9H, few surface defects for a long time after curing of coatingsThe adverse circumstances such as mist, coating securely reach 0 grade, are not easily stripped.
Specific embodiment
The present invention will be described in detail With reference to embodiment.
Embodiment 1
The present embodiment is related to a kind of titanium alloy bone inner fixing member with antimicrobial coating, wherein the coating of antimicrobial coating walksIt is rapid as follows:
1) titanium alloy bone inner fixing member is put into supersonic cleaning machine, uses acetone, ethyl alcohol, water each clear as cleaning solution respectivelyIt washes 1 time, each 20min, titanium alloy bone inner fixing member is then put into air dry oven dried for standby；
2) the titanium alloy bone inner fixing member after drying progress plasma surface in vacuum plasma machine is put into locate in advanceReason；Plasma surface pretreatment is carried out in two steps, and the gas system that the first step uses is carbon tetrafluoride and oxygen, gas flowThan for 1:2, the gas system that second step uses is oxygen, tetrahydrofuran and water, gas flow ratio 1:2:2, coprocessing 3min；
3) titanium alloy bone inner fixing member is exposed room temperature two days in air, then the poly- silicon of dip-coating by vacuum breaker afterAzane solution；Polysilazane solution includes coating substrate and solvent, wherein coating substrate is the organic poly- silicon of quaternary ammonium salt graft modificationAzane, solvent are n-butyl ether, and the mass fraction of quaternary ammonium salt graft modification organopolysilazane is 10%, time of immersion 10s；
4) titanium alloy bone inner fixing member is taken out after to be put into 80 DEG C, solidify 30min in the temperature and humidity case of 60% relative humidity；
5) finally titanium alloy bone inner fixing member is taken out from temperature and humidity case and is placed into vacuum oven, done at 40 DEG CDry 48h obtains the titanium alloy bone inner fixing member with antimicrobial coating.
Respectively using pencil hardometer and contact angle instrument testing coating pencil hardness and contact angle, and according to ISO2409-The adhesive force and antibiotic property of 2013 (or GB/T9286-1998) and ASTM-E2149-01 standard difference testing coating, carry out simultaneouslyInhibition zone test；The test that comparative example 1-1 and comparative example 1-2 carries out identical items is set, and comparative example 1-1 is uncoated processingTitanium alloy bone inner fixing member, comparative example 1-2 is exposure placement two days after common oxygen plasma treatment and in air,Then the titanium alloy bone inner fixing member of the above-mentioned identical antimicrobial coating of coating, test result are listed in table 1 again.
1 titanium alloy bone inner fixing member performance test of table
Above-mentioned test result shows: titanium alloy bone inner fixing member hydrophilicity and antibacterial ability after coating antimicrobial coating obtainPromotion is arrived, the hardness of coating is high, adhesive force is good, illustrates that coating bacteria-resistant version is that non-releasing micro is anti-without inhibition zone phenomenon is surroundBacterium；And after plasma two-step pretreatment coating coating, anti-microbial property is substantially better than comparative example 1-2 through general plasmaThe coating of coating after process.
Embodiment 2
The present embodiment is related to a kind of injector for medical purpose with lower resistance coating, wherein the coating step of lower resistance coatingIt is as follows:
1) take the 5ml polypropylene injector for medical purpose of aseptic packaging, extract syringe needle and core bar piston, be then placed in vacuum etc. fromPlasma surface pretreatment is carried out in daughter machine；Plasma surface pretreatment is carried out in two steps, the gas that the first step usesSystem is carbon tetrafluoride and oxygen, gas flow ratio 1:2, and the gas system that second step uses is glycol dimethyl ether, oxygenWith complementary gas ammonia, gas flow ratio 1:4:1, coprocessing 5min；
2) injector for medical purpose is exposed room temperature two days in air, poly- silicon nitrogen is then sprayed to it by vacuum breaker afterAlkane solution；Polysilazane solution includes coating substrate and solvent, wherein coating substrate is to change through nano silica physical mixedProperty inorganic polysilazane, solvent is butyl acetate, wherein the mass fraction of inorganic polysilazane and silica nanometer powder pointIt Wei 5% and 0.5%；Use nitrogen or argon gas as spraying boost gas, single carried out to syringe inner wall and is uniformly sprayed,Solution spraying amount is 100 μ l；
3) it after spraying, takes out syringe and is put into 25 DEG C, solidifies 2h in the temperature and humidity case of 60% relative humidity；
4) finally injector for medical purpose is taken out from temperature and humidity case and is placed into vacuum oven, the dry 48h at 40 DEG C,Obtain the injector for medical purpose with lower resistance coating.
According to GB15810-2001 and YY/T0909-2013 standard, lower resistance coating injection is tested using universal testing machineThe performance of device, and use the contact angle of contact angle instrument testing coating；Comparative example 2-1 is set and comparative example 2-2 does identical itemsTest, comparative example 2-1 are the injector for medical purpose of uncoated processing, and comparative example 2-2 is after common oxygen plasma treatmentAnd exposure is placed two days in air, then the injector for medical purpose of the above-mentioned lower resistance coating of coating, test result are listed in table 2 again.
2 injector for medical purpose performance test of table
Above-mentioned test result shows: injector for medical purpose makes core bar piston and syringe wall surface after coating lower resistance coatingFrictional force reduce, there is better self-lubricating property, while hydrophilicity, also obtaining with the affine performance of nonpolar liquidIt improves；And after plasma two-step pretreatment coating coating, properties are better than comparative example 2-2 through general plasmaThe coating of coating after process, comparative example 2-2 is in sliding property test because coating is uneven and larger (the plasma of roughnessSurface treatment imeliness problem causes), coating has the part obviously to fall off.
Embodiment 3
The present embodiment is related to a kind of silicone catheter with hydrophilic superslide coating, wherein the coating of hydrophilic superslide coatingSteps are as follows:
1) silicone catheter for taking aseptic packaging is directly placed into progress plasma surface in vacuum plasma machine and locates in advanceReason；Plasma surface pretreatment is carried out in two steps, and the gas system that the first step uses is octafluoropropane and carbon dioxide, gasFlow-rate ratio is 1:6, and the gas system that second step uses is butadiene, carbon dioxide and complementary gases argon, gas flow ratioFor 1:3:1, coprocessing 5min；
2) silicone catheter is exposed room temperature two days in air, then to the poly- silicon nitrogen of its dip-coating by vacuum breaker afterAlkane solution；Polysilazane solution includes coating substrate and solvent, wherein coating substrate is vinyl modified polysilazane, silaneCoupling agent KH570, n-vinyl pyrrolidone, polyethylene glycol dimethacrylate and Kollidon 90 it is mixedClose solution, solvent be dimethylformamide, formamide and ethyl acetate mixture, wherein vinyl modified polysilazane andThe mass fraction of silane coupling agent KH570 is respectively 1% and 0.5%, and substrate further includes 0.1% Karst catalyst(based on vinyl polysilazane quality)；Silicone catheter is lifted out with the speed of 3cm/min after dip-coating 120s；
3) after dip-coating, silicone catheter is put into 80 DEG C, solidifies 2h in the temperature and humidity case of 60% relative humidity；
4) finally silicone catheter is taken out from temperature and humidity case and is placed into vacuum oven, the dry 48h at 40 DEG C,Obtain the silicone catheter with hydrophilic superslide coating.
Respectively using the contact angle and friction system of contact angle instrument and friction coefficient instrument (200g sliding block) test silicone catheterNumber；Comparative example 3-1 and comparative example 3-2 is set and does the test of identical items, comparative example 3-1 is the silica gel urethral catheterization of uncoated processingPipe, comparative example 3-2 are exposure placement two days after common oxygen plasma treatment and in air, then the above-mentioned parent of coating againThe silicone catheter of water superslide coating, test result are listed in table 3.
3 silicone catheter performance test of table
Above-mentioned test result shows: it is good that silicone catheter is provided with silicone catheter after the hydrophilic superslide coating of coatingGood hydrophilicity, test dynamic friction coefficient reduces 90% or more under water environment, is resistant to 20 times or more frictions；And through etc.The coating of coating after gas ions two-step pretreatment, comprehensive performance are better than comparative example 3-2 after general plasma processThe coating of coating, comparative example 3-2 is after friction 10 times due to coating adhesion not enough (plasma surface treatment imeliness problemCause) and obvious delamination occurs, coefficient of friction increases.
Embodiment 4
The present embodiment is related to a kind of endoscope lens eyeglass with anti-fog coating, wherein the coating step of anti-fog coatingIt is as follows:
1) first using lens cleaning agent by endoscope lens eyeglass (diameter 10mm) clean 3 times, be then placed in vacuum etc. fromPlasma surface pretreatment is carried out in daughter machine；Plasma surface pretreatment is carried out in two steps, the gas that the first step usesSystem is carbon tetrafluoride and oxygen, gas flow ratio 1:3, the gas system that second step uses be butadiene and carbon dioxide,Gas flow ratio is 1:3, coprocessing 5min；
2) vacuum breaker after, is exposed to room temperature two days in air for endoscope eyeglass, then to the poly- silicon nitrogen of its spin coatingAlkane solution；Polysilazane solution includes coating substrate and solvent, wherein coating substrate is inorganic polysilazane, mono methoxy is poly-The mixed solution of glycolmethacrylate and nano-titanium dioxide, solvent are butyl acetate, wherein inorganic polysilazane andThe mass fraction of nano-titanium dioxide is respectively 8% and 1%, and substrate further includes that 5% piperazine or piperidines catalyst (are pressedInorganic polysilazane quality meter)；To each spin coating of endoscope objective lenses tow sides 2 times, spin coating rate 1000r/min, every timeSpin coating solution adding amount is 20 μ l；
3) after spin coating, endoscope lens eyeglass is put into 400 DEG C of high temperature furnace and solidifies 0.5h；
4) finally endoscope lens eyeglass is placed into vacuum oven from taking-up in high temperature furnace, it is dry at 40 DEG C48h obtains the endoscope lens eyeglass with anti-fog coating.
Respectively using pencil hardometer, the pencil hardness of contact angle instrument and light transmittance tester testing lens, contact angle andLight transmittance；The test that comparative example 4-1 and 4-2 do identical items is set, and comparative example 4-1 is the endoscope lens of uncoated processingEyeglass, comparative example 4-2 are placed two days to expose after common oxygen plasma treatment and in air, and then coating is antifog againThe endoscope lens eyeglass of coating, test result are listed in table 4；
The test of 4 endoscope lens lens performance of table
Above-mentioned test result shows: endoscope lens eyeglass obtains good Superhydrophilic after coating anti-fog coating,Durability is good, and coating hardness is high；And after plasma two-step pretreatment coating coating, anti-fogging durability can be better than comparisonThe coating of example 4-2 coating after general plasma process.
Embodiment 5
The present embodiment is related to a kind of ultrasound knife cutter head with anti-adhesive coating, wherein the coating step of anti-adhesive coatingIt is as follows:
1) ultrasound knife cutter head is put into supersonic cleaning machine, acetone, ethyl alcohol, water is used respectively to clean as cleaning solution respectively 1 time,Then ultrasound knife cutter head is put into vacuum oven dried for standby by each 20min；
2) the ultrasound knife cutter head after drying is put into progress plasma surface pretreatment in vacuum plasma machine；Deng fromDaughter surface preparation is carried out in two steps, and the gas system that the first step uses is perfluoroethane and oxygen, gas flow ratio 1:4, the gas system that second step uses is propylene oxide and oxygen, gas flow ratio 1:4, coprocessing 3min；
3) ultrasound knife cutter head is exposed room temperature two days in air, then to the poly- silicon nitrogen of its dip-coating by vacuum breaker afterAlkane solution；Polysilazane solution includes coating substrate and solvent, wherein coating substrate is methyl polysilicon azane and perfluoro decyl thirdOlefin(e) acid ester, solvent are butyl acetate, wherein the mass fraction of methyl polysilicon azane is 15%, and substrate further includes 0.1%Karst catalyst (based on methyl polysilicon azane quality), dip-coating 1min；
3) after dip-coating, the vacuum oven inside holding 4h that ultrasound knife cutter head is put into 80 DEG C is taken out, is then transferred to 110 againDEG C, solidify 1h in the temperature and humidity case of 60% relative humidity；
4) finally ultrasound knife cutter head is taken out from temperature and humidity case and is placed into vacuum oven, the dry 48h at 40 DEG C,Obtain the ultrasound knife cutter head with anti-adhesive coating.
Respectively using the pencil hardness and contact angle of pencil hardometer and contact angle instrument test cutter head coating, and use FITCFluorescent marker method tests the adherency situation of blood platelet and fibrinogen in vitro；Setting comparative example 5-1 and comparative example 5-2 does phaseWith the test of project, comparative example 5-1 is the ultrasound knife cutter head of uncoated processing, and comparative example 5-2 is to pass through common oxygen plasmaIt exposes after body processing and in air and places two days, then the ultrasound knife cutter head of coating anti-adhesive coating, test result are listed in againTable 5.
5 ultrasound knife cutter head performance test of table
Above-mentioned test result shows: ultrasound knife cutter head is provided with the ability of anti-tissue adhension after coating anti-adhesive coating,Coating hardness is high simultaneously, has good hydrophobic performance and reprimand nonpolar liquid, further avoids the contamination of sufferer body fluid；And after plasma two-step pretreatment coating coating, anti-adhesive properties are better than comparative example 5-2 through general plasma workThe coating of coating after skill processing.
It is emphasized that: the above is only presently preferred embodiments of the present invention, not make in any form to the present inventionLimitation, any simple modification, equivalent change and modification to the above embodiments according to the technical essence of the invention,All of which are still within the scope of the technical scheme of the invention.