阅读说明：本技术 一种医用介入材料亲水润滑涂层的制备方法 (A kind of preparation method of medical intervention material hydrophilic lubrication coating ) 是由 郭熙海 于 2019-08-02 设计创作，主要内容包括：本发明涉及一种医用介入材料亲水润滑涂层的制备方法,属于医用材料技术领域。本发明以O<Sub>2</Sub>和NH<Sub>3</Sub>作为工作气体,对环氧树脂进行等离子体处理,在处理后的表面接枝泥鳅滑液,将接枝物紫外固化在基体表面上,制备出一种医用介入材料亲水润滑涂层,泥鳅滑液中含有泥鳅多糖,该多糖对活性氧具有直接清除作用,因此具有良好的抗炎症效果,环氧树脂在经过等离子体处理后,使得亲水性和表面湿润性得到改善,制备的医用介入材料亲水润滑涂层具有良好的亲水润滑性和抗炎作用；等离子体处理过程的气体是引入官能团的供体,经等离子体处理后的,在表面引入像羟基(-OH)、氨基(-NH2)等极性基团,然后亲水高分子与活性基团接枝,来提高材料表面的亲水性。(The present invention relates to a kind of preparation methods of medical intervention material hydrophilic lubrication coating, belong to medical material tech field.The present invention is with O 2 And NH 3 As working gas, corona treatment is carried out to epoxy resin, surface grafting beardie mucus after treatment, by graft ultra-violet curing on matrix surface, prepare a kind of medical intervention material hydrophilic lubrication coating, contain Misgurnus anguillicaudatus polysaccharides in beardie mucus, the polysaccharide has direct scavenging effect to active oxygen, therefore there is good anti-inflammatory effect, epoxy resin is after corona treatment, so that hydrophily and surface moist are improved, the medical intervention material hydrophilic lubrication coating of preparation has good Hydrophilic lubrication and anti-inflammatory effect；The gas of plasma treatment procedure is the donor for introducing functional group, plasma treated, is introduced on surface as hydroxyl (- OH), amino (- NH2) isopolarity group, then hydrophilic high mol and active group are grafted, the hydrophily of Lai Tigao material surface.)

1. a kind of preparation method of medical intervention material hydrophilic lubrication coating, it is characterised in that specific preparation step are as follows:

(1) epoxy resin is placed in plasma apparatus, corona treatment is to get pretreatment epoxy resin；

(2) phosphate buffer solution for taking pretreatment epoxy resin, beardie mucus, 0.1mol/L will pre-process epoxy resin, mud The phosphate buffer solution of loach synovia and 0.1mol/L mix, and after stir process, are rapidly cooled to room temperature to get reaction solution；

(3) reaction solution and deionized water are mixed, carries out dialysis treatment to get dialyzate, dialyzate is placed in freeze drier In, vacuum freeze drying processing is to get graft；

(4) graft, polyamide curing agent, photoinitiator triaryl sulphur hexafluoro antimonate, reactive diluent propylene oxide are taken Butyl ether, by graft, polyamide curing agent, photoinitiator triaryl sulphur hexafluoro antimonate and reactive diluent propylene oxide Butyl ether mixing, stir process is to get compo；

(5) compo is coated uniformly on medical intervention material surface, is dried to get semi-finished product, semi-finished product is placed in In ultraviolet light curing apparatus between two ultraviolet lamps, ultraviolet irradiation processing is to get medical intervention material hydrophilic lubrication coating.

2. a kind of preparation method of medical intervention material hydrophilic lubrication coating according to claim 1, it is characterised in that: step Suddenly plasma treatment step described in (1) are as follows: epoxy resin is placed in plasma apparatus, with O₂And NH₃As work gas Body is 100~120Pa in pressure, and power is 45~60s of corona treatment under 300~350W.

3. a kind of preparation method of medical intervention material hydrophilic lubrication coating according to claim 1, it is characterised in that: step Suddenly the ratio between the phosphate buffer solution of pretreatment epoxy resin, beardie mucus, 0.1mol/L described in (2) is respectively as follows: According to parts by weight, 20~30 parts of pretreatment epoxy resin, 10~20 parts of beardie mucus, 50~60 parts of 0.1mol/L are weighed respectively Phosphate buffer solution.

4. a kind of preparation method of medical intervention material hydrophilic lubrication coating according to claim 1, it is characterised in that: step Suddenly stir process step described in (2) are as follows: the phosphate buffer solution of epoxy resin, beardie mucus and 0.1mol/L will be pre-processed Mixing is 60~100 DEG C in temperature, and mixing speed is that 30~50min is stirred under 150~200r/min.

5. a kind of preparation method of medical intervention material hydrophilic lubrication coating according to claim 1, it is characterised in that: step Suddenly dialysis treatment step described in (3) are as follows: 1: 100 reaction solution and deionized water are mixed by volume, are 4~6 DEG C in temperature It is lower dialysis 20~for 24 hours.

6. a kind of preparation method of medical intervention material hydrophilic lubrication coating according to claim 1, it is characterised in that: step Suddenly vacuum freeze drying processing step described in (3) are as follows: dialyzate is placed in freeze drier, is -40~-50 DEG C in temperature 5~8h of lower vacuum freeze drying.

7. a kind of preparation method of medical intervention material hydrophilic lubrication coating according to claim 1, it is characterised in that: step Suddenly graft, polyamide curing agent described in (4), photoinitiator triaryl sulphur hexafluoro antimonate, reactive diluent epoxy third Ratio between alkane butyl ether is respectively as follows: according to parts by weight, weighs 80~100 parts of grafts, 50~60 parts of polyamide respectively Curing agent, 20~40 parts of photoinitiator triaryl sulphur hexafluoro antimonates, 10~12 parts of reactive diluent epoxy propane butyl ethers.

8. a kind of preparation method of medical intervention material hydrophilic lubrication coating according to claim 1, it is characterised in that: step Suddenly stir process step described in (4) are as follows: by graft, polyamide curing agent, photoinitiator triaryl sulphur hexafluoro antimonate It is mixed with reactive diluent epoxy propane butyl ether, low whipping speed is that 10~20min is stirred under 300~350r/min.

9. a kind of preparation method of medical intervention material hydrophilic lubrication coating according to claim 1, it is characterised in that: step Suddenly drying process step described in (5) are as follows: compo is coated uniformly on medical intervention material surface, being placed in temperature is 60 Dry 30~40min at~70 DEG C.

10. a kind of preparation method of medical intervention material hydrophilic lubrication coating according to claim 1, it is characterised in that: Ultraviolet irradiation processing step described in step (5) are as follows: semi-finished product are placed in ultraviolet light curing apparatus between two ultraviolet lamps, spoke Penetrating distance is 10~12cm, and dual light shines 3~5min.

Technical field

The present invention relates to a kind of preparation methods of medical intervention material hydrophilic lubrication coating, belong to medical material technology neck Domain.

Background technique

Interventional therapy is a kind of new technology for growing rapidly to get up in recent years, it indicates the new page of medical field. Interventional therapy is under the guiding of the medical imaging equipments such as fluoroscopic machine, angiography machine, CT, B ultrasound, by medical catheter, seal wire etc. Accurate medical instrument reaches the medical skill that human lesion position carries out diagnosis and local treatment by human vas, stomach tube, urethra Art.The small wound of 1 ~ 2mm is opened using local anaesthesia and only in human body surface because carrying out interventional therapy, intervention is controlled Treatment is compared with traditional surgical operation to be haveed many advantages, such as, for example is reduced the difficulty of operation, improved the efficiency performed the operation, mitigate patient The pain of operation shortens patient's hospital stays and post-operative recovery is fast, especially substantially reduces the expense of hospital and patient's operation.Always For it, intervention operation be vast sufferer bringing Gospel.Interventional medical device is as the doctor to grow up with interventional therapy Treat an important branch figure of instrument, the also favor increasingly by numerous researchers of relative project.

In vascular interventional treatment, the effect of interventional guide wire during surgery includes: that guiding catheter through epidermis enters blood vessel；Association Assistant director of a film or play's pipe selectively enters minute blood vessel branch or other lesion lacunas；Replace the important tool of conduit.Therefore, when seal wire into Blood vessel and when moving in the blood vessel out, the surface of high-lubricity is it is possible to prevente effectively from plasma protein, blood platelet etc. exist in blood The adherency of material surface mitigates the damage to haemocyte and vascular wall, reduces the interference moved to blood laminar flow, while can press down The generation of Coagulation test processed.Although high hydrophobicity and super hydrophilic surface can generate greasy property, due to intervening class device Tool is directly contacted with body fluid, and body fluid will infiltrate medical instrument.So if it is desired that there is low friction when instrument with contacting in vivo Power or instrument need to be soaked by body fluid not to be contaminated but, or is the formation of bubble in order to prevent, and high water-wetted surface is more suitable for. But the outer layer high molecular material for making seal wire is mostly hydrophobic, such as polyurethane (TPU), polyetheramides (Pebax), full fluorine copolymer (FEP) etc..Therefore seal wire surface is made to reach Hydrophilic lubrication right and wrong by surface hydrophilic modification Often it is necessary to.

Ideal bio-medical material should have good lubricity and biocompatibility.Due to the process in intervention human body In, bio-medical material inevitably can generate friction with the tissue of human body or blood vessel, will when this frictional force is larger Epithelial tissue is caused to damage, the pain of caused patient or sense of burning, while the tissue being damaged also bacterium easy to breed, and Cause inflammation.Therefore, lubricity is one of highly important performance of intervention material.Lubricity processing is done to intervention material surface, Material can be made into human body and when body fluid contact becomes quite to lubricate, mitigating the pain of patient to the maximum extent, while can be with The absorption for efficiently reducing bacterial adhesion and protein is the main path for improving material surface biocompatibility.When intervention material Material when entering, exiting blood vessel and move in the blood vessel, high-lubricity can inhibit macromolecular such as plasma protein in blood, The adherency on the surface of the material such as blood platelet reduces the damage to vascular wall and haemocyte, mitigates the disturbance moved to blood laminar flow, together When can avoid Coagulation test generation.Therefore, very necessary to intervention material progress surface lubrication processing.Coating hydrophilic coating is Improve the effective means of intervention material greasy property.Hydrophilic superslide coating is made by hydrogel, the biomembrane on similar loach surface, Dedicated for medical instrument.The coating can adsorb and save moisture, significantly reduce frictional force, have extraordinary lubricating action. The sense of discomfort of patient can effectively be mitigated and avoid the complication due to caused by mucous membrane and tissue cell insult in insertion process.

Therefore it needs this kind of hydrophilic coating that there is high lubricity, can be improved blood compatibility, reduce the damage to tissue Wound；Lower coefficient of friction can be kept for a long time.

Summary of the invention

The technical problems to be solved by the invention: for during intervening human body, bio-medical material can not be kept away It is exempting to generate friction with human body tissue or blood vessel, epithelial tissue will be caused to damage when this frictional force is larger, caused Patient pain or sense of burning, while the tissue being damaged also bacterium easy to breed, and the problem of cause inflammation, provide one The preparation method of the medical intervention material hydrophilic lubrication coating of kind.

In order to solve the above technical problems, the technical solution adopted by the present invention is that:

(1) epoxy resin is placed in plasma apparatus, corona treatment is to get pretreatment epoxy resin；

(2) phosphate buffer solution for taking pretreatment epoxy resin, beardie mucus, 0.1mol/L will pre-process epoxy resin, mud The phosphate buffer solution of loach synovia and 0.1mol/L mix, and after stir process, are rapidly cooled to room temperature to get reaction solution；

(3) reaction solution and deionized water are mixed, carries out dialysis treatment to get dialyzate, dialyzate is placed in freeze drier In, vacuum freeze drying processing is to get graft；

(4) graft, polyamide curing agent, photoinitiator triaryl sulphur hexafluoro antimonate, reactive diluent propylene oxide are taken Butyl ether, by graft, polyamide curing agent, photoinitiator triaryl sulphur hexafluoro antimonate and reactive diluent propylene oxide Butyl ether mixing, stir process is to get compo；

(5) compo is coated uniformly on medical intervention material surface, is dried to get semi-finished product, semi-finished product is placed in In ultraviolet light curing apparatus between two ultraviolet lamps, ultraviolet irradiation processing is to get medical intervention material hydrophilic lubrication coating.

Plasma treatment step described in step (1) are as follows: epoxy resin is placed in plasma apparatus, with O₂And NH₃ It is 100~120Pa in pressure, power is 45~60s of corona treatment under 300~350W as working gas.

Ratio between the phosphate buffer solution of pretreatment epoxy resin, beardie mucus, 0.1mol/L described in step (2) Example is respectively as follows: according to parts by weight, weighs 20~30 parts of pretreatment epoxy resin, 10~20 parts of beardie mucus, 50~60 respectively The phosphate buffer solution of part 0.1mol/L.

Stir process step described in step (2) are as follows: the phosphoric acid of epoxy resin, beardie mucus and 0.1mol/L will be pre-processed Salt buffer solution mixing is 60~100 DEG C in temperature, and mixing speed is that 30~50min is stirred under 150~200r/min.

Dialysis treatment step described in step (3) are as follows: mix reaction solution and deionized water at 1: 100 by volume, in temperature Degree is dialysis 20 at 4~6 DEG C~for 24 hours.

Vacuum freeze drying processing step described in step (3) are as follows: dialyzate is placed in freeze drier, in temperature It is 5~8h of vacuum freeze drying at -40~-50 DEG C.

Graft described in step (4), polyamide curing agent, photoinitiator triaryl sulphur hexafluoro antimonate, activity are dilute The ratio between agent epoxy propane butyl ether is released to be respectively as follows: according to parts by weight, weigh respectively 80~100 parts of grafts, 50~ 60 parts of polyamide curing agents, 20~40 parts of photoinitiator triaryl sulphur hexafluoro antimonates, 10~12 parts of reactive diluent epoxies Propane butyl ether.

Stir process step described in step (4) are as follows: by graft, polyamide curing agent, photoinitiator triaryl sulphur Hexafluoro antimonate and reactive diluent epoxy propane butyl ether mixing, low whipping speed be 300~350r/min under stirring 10~ 20min。

Drying process step described in step (5) are as follows: compo is coated uniformly on medical intervention material surface, juxtaposition It is that 30~40min is dried at 60~70 DEG C in temperature.

Ultraviolet irradiation processing step described in step (5) are as follows: by semi-finished product be placed in ultraviolet light curing apparatus two it is ultraviolet Between lamp, radiation length is 10~12cm, and dual light shines 3~5min.

The present invention is compared with other methods, and advantageous effects are:

(1) present invention is with O₂And NH₃As working gas, corona treatment is carried out to epoxy resin, surface after treatment Grafting beardie mucus prepares a kind of medical intervention material hydrophilic lubrication coating by graft ultra-violet curing on matrix surface, Contain Misgurnus anguillicaudatus polysaccharides in beardie mucus, is made of a high glycan and oligosaccharides, which has direct scavenging effect to active oxygen, Therefore there is good anti-inflammatory effect, epoxy resin is after corona treatment, so that hydrophily and surface moist Improved, the medical intervention material hydrophilic lubrication coating of preparation has good Hydrophilic lubrication and anti-inflammatory effect；

(2) plasma technology of the present invention is a general, effective technology, its important application is surface modification Or activation, the gas of plasma treatment procedure is the donor for introducing functional group, for example generates amido functional group with ammonia, is passed through After corona treatment, introduce on surface as hydroxyl (- OH), amino (- NH2) isopolarity group, then hydrophilic high mol with Active group grafting, the hydrophily of Lai Tigao material surface；

(3) contain Misgurnus anguillicaudatus polysaccharides, SOD and microelement in beardie mucus of the present invention, loach has liver protection except Huang, clearing heat and detoxicating The effect of, beardie mucus has the active constituent of liver protection effect, and Misgurnus anguillicaudatus polysaccharides can obviously inhibit mouse caused by thioacetamide Transaminase activity and hepatomegaly in serum can also obviously inhibit Cyklokapren activity and icterus index in serum to increase, and significantly drop Low liver swelling and bile pent-up have the function of anti-inflammatory, transaminase lowering, except jaundice；K rich in beardie mucus, The microelements such as Na, Mg, Fe, Zn, Cu, Mn, Se, the wherein content highest of K and Na, Fe, Zn, Mn, Se are intracorporal to biology to exempt from Epidemic disease system is coordinated and is controlled to organism metabolism function by enzyme system, improved the immunity of body, reach with to connect effect To antibacterial and antiviral effect；

(4) epoxy resin is a kind of important ultraviolet photo-curing cementing agent material, C-C in epoxide resin polymer chain in the present invention Key and ehter bond ensure that chemical resistance, epoxy group and hydroxyl access beardie mucus as reflecting point, with ultraviolet Photocuring activity and good adhesiveness promote its adsorption capacity to metallic substrate surface and polar substances；

(5) ultra-violet curing technology is to belong to chemical method by ultraviolet light-initiated chemical reaction in the present invention, can be in several seconds, number It is solidified into product in minute, production efficiency can be significantly improved, save production cost, ultra-violet curing belongs to low-temperature setting, thus can Avoid high temperature on influence caused by thermo-responsive matrix (especially plastic products) (such as deformation, decomposition etc.).

Specific embodiment

Epoxy resin is placed in plasma apparatus, with O₂And NH₃It is 100~120Pa in pressure as working gas, Power is 45~60s of corona treatment under 300~350W to get pretreatment epoxy resin；According to parts by weight, it weighs respectively The phosphate buffer solution of 20~30 parts of pretreatment epoxy resin, 10~20 parts of beardie mucus, 50~60 parts of 0.1mol/L, will be pre- The phosphate buffer solution mixing for handling epoxy resin, beardie mucus and 0.1mol/L is 60~100 DEG C in temperature, stirring speed Degree is after stirring 30~50min under 150~200r/min, to be rapidly cooled to room temperature to get reaction solution；It incites somebody to action at 1: 100 by volume Reaction solution and deionized water mixing, temperature be 4~6 DEG C at dialysis 20~for 24 hours to get dialyzate, dialyzate is placed in freezing In drying machine, 5~8h of vacuum freeze drying is at being -40~-50 DEG C in temperature to get graft；According to parts by weight, claim respectively Take 80~100 parts of grafts, 50~60 parts of polyamide curing agents, 20~40 parts of photoinitiator triaryl sulphur hexafluoro antimonates, 10~12 parts of reactive diluent epoxy propane butyl ethers, by graft, photoinitiator triaryl sulphur hexafluoro antimonate and activity The mixing of diluent epoxy propane butyl ether, low whipping speed are that 10~20min of stirring applies under 300~350r/min to get mixing Material, is coated uniformly on medical intervention material surface for compo, and being placed in temperature is dry 30~40min at 60~70 DEG C, Up to semi-finished product, semi-finished product are placed in ultraviolet light curing apparatus between two ultraviolet lamps, radiation length is 10~12cm, two-sided 3~5min of illumination is to get medical intervention material hydrophilic lubrication coating.