CN106540336A - A kind of hydrophilic modifying coating on medical introducing duct surface - Google Patents
A kind of hydrophilic modifying coating on medical introducing duct surface Download PDFInfo
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- CN106540336A CN106540336A CN201611073783.1A CN201611073783A CN106540336A CN 106540336 A CN106540336 A CN 106540336A CN 201611073783 A CN201611073783 A CN 201611073783A CN 106540336 A CN106540336 A CN 106540336A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/08—Materials for coatings
- A61L29/085—Macromolecular materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/04—Macromolecular materials
- A61L29/041—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/04—Macromolecular materials
- A61L29/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
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Abstract
The invention discloses a kind of hydrophilic modifying coating on medical introducing duct surface, the hydrophilic modifying coating is made up of transition coating and lubrication coating, and the parts by weight of the composition and each component of transition coating are：5 10 parts of binding resin, I 0.1 0.2 parts of light trigger, 0.05 0.1 parts of levelling agent, I 85 95 parts of solvent；The composition and the parts by weight of each component of lubrication coating be：5 10 parts of hydrophilic resin, 15 parts of water cross-linking agent, II 0.2 0.5 parts of light trigger, II 80 95 parts of solvent.The present invention includes that transition zone and lubricating layer are light solidifying coating, and the curing of coatings time is short, and consumed energy is low, and convenient batch production.
Description
Technical field
The present invention relates to a kind of hydrophilic modifying coating on medical introducing duct surface, belongs to medical introducing duct field.
Technical background
Interposing catheter is one of the most frequently used medical apparatus and instruments and consumptive material in medical procedure, its conventional base material be polyurethane,
Polrvinyl chloride, polyester etc., these materials are hydrophobic material, and bonding occurs between tissue easily in use and disease is caused
The pain of trouble, and easily cause infection.Hydrophilic modification is carried out to interposing catheter, its lubricity can be improved, reduce interposing catheter
The sense of discomfort of sufferer when in use, while improving the safety in utilization of interposing catheter.
With regard to the design of interposing catheter hydrophilic modifying and hydrophilic coating, there are substantial amounts of patent report, such as patent in the country
CN102993407A discloses a kind of method of monolayer hydrophilic coating modified polyurethane, and the method synthesizes a kind of poly- ammonia of aqueouss first
Then ester is prepared for photocureable coating, hydrophilic painting prepared by the method with NVP, vinyl organosilicon copolymerization
There may be NVP monomer residues after layer solidification, and coefficient of friction is larger after aquation；Patent CN104448375A discloses a kind of silica
The method that PVP is coated to into PVC catheter surfaces after alkane is coupling agent modified, coefficient of friction after hydrophilic coating aquation prepared by the method
It is relatively low but adhesive force is poor；Patent CN103933616A disclose it is a kind of by conduit after plasma process graft acrylic acid,
The method of modifying of the subbing and the surface coating material containing polymethyl vinyl ether-maleic anhydride of aqueous polyurethane is then coated with,
Hydrophilic coating adhesive force that the method is obtained is good but due to needing to be neutralized with strong aqua ammonia containing acidic-group, and preparation process mistake
Many, processing procedure is comparatively laborious.Patent CN103289499A discloses a kind of polymer chain and contains the hydrophilic of optical active group
Resin and the method for preparing photocuring hydrophilic coating containing photolytic activity cross-linking agent, the method are hardening time short, but in preparation process
Need to synthesize special photoreactive resin, production of resins and purge process are loaded down with trivial details, and production cost is higher.
Therefore, develop a kind of material to be easy to get, produce curing easy quick, good biocompatibility, adhesive force and lubrication
Function admirable and lower-cost hydrophilic lubrication coating is very important.
The content of the invention
It is an object of the invention to provide a kind of hydrophilic modifying coating on medical introducing duct surface.
A kind of hydrophilic modifying coating on medical introducing duct surface, it is characterised in that the hydrophilic modifying coating is applied by transition zone
Material and lubrication coating composition, the composition of transition coating and the parts by weight of each component are：Binding resin 5-10 parts,
I 0.1-0.2 parts of light trigger, levelling agent 0.05-0.1 parts, I 85-95 parts of solvent；The composition and each group of the lubrication coating
Point parts by weight be：Hydrophilic resin 5-10 parts, water cross-linking agent 1-5 parts, II 0.2-0.5 parts of light trigger, II 80- of solvent
95 parts.
The binding resin is unsaturated acrylic resin, one or two mixed in unsaturated polyurethanes acrylate
Compound.
The light trigger I is 1- hydroxycyclohexyl phenyl ketones, 2- hydroxyl -4'- (2- hydroxy ethoxies) -2- methyl phenylpropyl alcohols
One or two compositionss in ketone, 2- hydroxy-2-methyl -1- phenyl -1- acetone.
The levelling agent be Bi Ke companies production BKY 333, Dow Corning Corporation production DC57 in one or two
Mixture.
The solvent I is ethanol, isopropanol, one or two the mixture in ethyl acetate.
The hydrophilic resin is Polyethylene Glycol（PEG）, polyvinyl alcohol（PVA）, it is polyvinylpyrrolidone (PVP), transparent
One or more group in matter acid, NVP-hydroxyethyl methylacrylate copolymer (PVP-PHEMA)
Compound.
The water cross-linking agent is polyethyleneglycol diacrylate（PEG600DA or PEG400DA）.
The light trigger II is 1- hydroxycyclohexyl phenyl ketones, 2- hydroxyl -4'- (2- hydroxy ethoxies) -2- methylbenzene
One or more mixture in acetone, 2- hydroxy-2-methyl -1- phenyl -1- acetone, benzophenone.
The solvent II is methanol, ethanol, the two or more mixture in isopropyl alcohol and water.
The using method of the hydrophilic modifying coating on medical introducing duct surface is as mentioned above：Will be Jing ethanol purges clean
Conduit is soaked the 10-30 seconds in transition coating, then completes application with the speed lifting of 1.0-1.5 cels, in 1000 W
Uviol lamp under irradiate the 30-60 seconds obtain final product transition zone；The conduit for having been completed transition zone application soaks 10- in lubrication coating
30 seconds, after then being lifted with the speed of 0.5-1.0 cels, under the uviol lamp of 400 W, the irradiation 150-210 seconds were curable
Completely.
The material of the conduit is polyurethane, polrvinyl chloride or polyester.
The transition zone contained double bond after ultraviolet light is not reacted completely, the ability after solidifying through lubricating layer
React completely, therefore have chemical bond between transition zone and lubricating layer cross-linking agent, improve between transition zone and lubricating layer
Interaction force.
Inierpeneirating network structure is formed between hydrophilic resin and water cross-linking agent in the lubricating layer, therefore which maintains
The good hydrophilic lubrication performance of resin itself, simultaneously because being crosslinked agent constraint so as to good adhesive force.
The interposing catheter surface hydrophilic lubricating layer lubricity and Detection of Stability method are：One is inserted in catheter interior
Diameter and the steel column of catheter diameter formed objects, make catheter shape keep constant, conduit are horizontally fixed on the tank for filling water
In, in sound tester for friction between after soaking 30 seconds（14WF, Japanese Shimadzu）On with silica gel piece as antithesis, in different loads with 0.5
The speed of cel carries out reciprocating friction experiment respectively.
The present invention have the advantage that compared with prior art for：
1st, the present invention includes that transition zone and lubricating layer are light solidifying coating, and the curing of coatings time is short, and consumed energy is low, and convenient
Batch production.
2nd, the present invention does not contain small molecule monomer and acidic-group, in production without the need for the step of removing unreacted monomer is set with
And neutralization reaction step, production method is simplified, production cost is reduced, while improve the safety that product is used.
3rd, there is chemical bond between transition zone of the present invention and lubricating layer, lubricating layer is internally formed interpenetrating networks knot
Structure, biocompatibility is good, maintain hydrophilic resin good hydrophilic lubrication performance while improve the adhesive force of lubricating layer.
4th, still there is low coefficient of friction after coating moistening of the present invention under compared with big load, and good stability, repeatedly
Excellent stability and ultralow coefficient of friction are kept after friction still.
Specific embodiment
A kind of hydrophilic modifying coating on medical introducing duct surface, the hydrophilic modifying coating is by transition coating and lubricating layer
Coating is constituted, and the preparation method of transition coating and lubrication coating is as follows：
The preparation of transition coating：5-10 part binding resins are added in 50 parts of solvents I, is added under the conditions of lucifuge after being sufficiently stirred for
Enter 0.1-0.2 parts light trigger I, after to be triggered dose of dissolving completely, add 35-45 parts solvent I, adjustment viscosity to 4.0-5.0
0.05-0.1 part levelling agents are added after mPas, is continued stirring 30 minutes, is packaged spare；
The preparation of lubrication coating：0.2-0.5 parts light trigger II is added in 70-80 parts solvent II, it is even after fully dissolving
Speed stirring is lower to add 5-10 parts hydrophilic resin and 1-5 part water cross-linking agents to be sufficiently stirred for 5-8 hours, after uniform solution to be formed
Measurement viscosity, adjusts viscosity to 90-120 mPas with 10-25 parts solvent II.
A kind of application of the hydrophilic modifying coating on medical introducing duct surface, comprises the steps：
Transition zone application：Dry up after interposing catheter is cleaned up in medical ethanol, by pulling machine by conduit with 3 centimetres/
In the speed immersion transition coating of second, soak 10-30 second, then complete to apply with the speed lifting of 1.0-1.5 cels
Dress, is transferred quickly under the uviol lamp of 1000 W, irradiates the 30-60 seconds, is placed in and hangs on clean place, it is to avoid conduit is mutual after taking-up
Contact；
Lubricating layer application：The conduit pulling machine for having been completed transition zone application is immersed in lubricating layer with the speed of 3 cels
Soak 10-30 second in coating, then with the lifting of the speed of 0.5-1.0 cels after, be transferred quickly to be provided with 400 W ultraviolet
In the solidification case of lamp, the irradiation 150-210 seconds can completion of cure.
A kind of its lubricity of medical introducing duct surface hydrophilic lubricating layer and Detection of Stability method are：Insert in catheter interior
Enter the steel column of and catheter diameter formed objects, make catheter shape keep constant, conduit is horizontally fixed on the water for filling water
In groove, in sound tester for friction between after soaking 30 seconds（14WF, Japanese Shimadzu）On with silica gel piece as antithesis, under different loads with
The speed of 0.5 cel carries out reciprocating friction experiment respectively.
The present invention is conducted further description with specific embodiment below：
Embodiment 1
Coating preparation：
10 parts of unsaturated acrylic resins are added in 50 parts of ethyl acetate, after being sufficiently stirred for, 0.2 part are added under the conditions of lucifuge
2- hydroxyl -4'- (2- hydroxy ethoxies) -2- methyl phenyl ketones, add 43 parts of isopropanols after to be triggered dose of dissolving completely, measure solution
Viscosity is 4.5 mPas, adds 0.1 part of levelling agent BYK333 to continue stirring 30 minutes, obtains transition coating；In 50 parts of second
0.3 part of benzophenone is added in alcohol and 25 parts of methanol, at the uniform velocity stir after fully dissolving it is lower add 3.5 parts of PVP, 1.5 parts of PEG and
1.0 parts of water cross-linking agent PEG400DA are sufficiently stirred for 7-8 hours, measure viscosity after uniform solution to be formed, with 10-20 part ethanol
Adjustment viscosity obtains lubricating coating to 90-95 mPas.
Coating process：
Interposing catheter is cleaned up in medical ethanol and is dried up, in the speed immersion by pulling machine by conduit with 3 cels
State in the transition coating of preparation, the speed lifting after soaking 10 seconds with 1.0 cels completes application, is transferred quickly to
Under the uviol lamp of 1000W, irradiate 30 seconds, be placed in after taking-up and hang on clean place, it is to avoid conduit contacts with each other；Then completed
The conduit of transition zone application will be immersed in the speed of 3 cels in the lubrication coating of above-mentioned preparation by pulling machine and be soaked
30 seconds, after then lifting with the speed of 1.0 cels, it is transferred quickly to be provided with irradiation 180 in the solidification case of 400W uviol lamps
Completion of cure by second.
Performance test：
The steel column of one and catheter diameter formed objects is inserted in catheter interior, makes catheter shape keep constant, by conduit level
It is fixed in the tank for filling water, in sound tester for friction between after soaking 30 seconds（14WF, Japanese Shimadzu）On be right with silica gel piece
It is even, reciprocating friction is carried out respectively with the speed of 0.5 cel respectively under the g load of 100 g, 300 g, 500 and tested for 20 cycles,
The average friction coefficient for obtaining is respectively 0.020,0.023,0.028.
Embodiment 2
Coating preparation：
8 parts of unsaturated polyurethanes acrylates are added in 25 parts of isopropanols and 25 parts of alcohol mixeding liquids, after being sufficiently stirred for
0.2 part of 2- hydroxy-2-methyl -1- phenyl -1- acetone is added under the conditions of lucifuge, after to be triggered dose of dissolving completely, 40 parts of second is added
Alcohol, measurement solution viscosity are 5 mPas, add 0.05 part of levelling agent DC57, continue stirring 30 minutes, obtain transition coating；
0.5 part of 2- hydroxyl -4'- (2- hydroxy ethoxies) -2- methyl phenyl ketone is added in 40 parts of water and 30 points of alcohol mixeding liquids, is treated fully
Lower addition 0.5 part PVA is stirred after dissolving at the uniform velocity, 5.0 parts of PVP-PHEMA copolymers and 1.0 parts of water cross-linking agent PEG600DA fill
Divide stirring 7-8 hours, after uniform solution to be formed, measure viscosity, viscosity is adjusted to 110-120 mPas with 15-25 parts ethanol,
Obtain lubricating coating.
Coating process：
Interposing catheter is cleaned up in medical ethanol, conduit is immersed with the speed of 3 cels by above-mentioned system by pulling machine
In standby transition coating, soak 20 seconds, application is completed with the speed lifting of 1.5 cels then, is being transferred to rapidly
Under the uviol lamp of 1000W, irradiate 30 seconds, be placed in after taking-up and hang on clean place, it is to avoid conduit contacts with each other；Then completed
The conduit of transition zone application will be immersed in the speed of 3 cels in the lubrication coating of above-mentioned preparation by pulling machine and be soaked
30 seconds, then with the lifting of the speed of 0.5 cel after, irradiate being transferred to be provided with the solidification case of 400W uviol lamps rapidly
210 seconds can completion of cure.
Performance test：
In method shown in embodiment 1, carried out with the speed of 0.5 cel respectively under the g load of 100 g, 300 g, 500 respectively
Reciprocating friction tested for 20 cycles, and the average friction coefficient for obtaining is respectively 0.018,0.022,0.029.
Embodiment 3
Coating preparation：
10 parts of unsaturated polyurethanes acrylates are added in 30 parts of isopropanols and 20 parts of ethyl acetate mixtures, is fully stirred
0.1 part of 2- hydroxy-2-methyl -1- phenyl -1- acetone and 0.1 part of 1- hydroxycyclohexylphenyl first are added after mixing under the conditions of lucifuge
Ketone, adds 38 parts of isopropanols after to be triggered dose of dissolving completely, measurement solution viscosity is 4.3 mPas, adds 0.05 part of levelling agent
BYK333, continues stirring 30 minutes, obtains transition coating；Add in 30 parts of ethanol, 20 parts of methanol and 20 parts of water mixed liquids
0.3 part of 1- hydroxycyclohexyl phenyl ketone and 0.2 part of 2- hydroxy-2-methyl -1- phenyl -1- acetone, after fully dissolving at the uniform velocity
Stirring is lower to add 2.0 parts of Polyethylene Glycol（PEG）, 5.5 parts of polyvinylpyrrolidone (PVP), 0.5 part of hyaluronic acid and 2.0 parts of water
Property cross-linking agent PEG600DA be sufficiently stirred for 7-8 hours, measure viscosity after uniform solution to be formed, and adjusted with 10-25 parts ethanol
Viscosity obtains lubricating coating to 100-110 mPas.
Coating process：
Interposing catheter is cleaned up in medical ethanol, conduit is immersed with the speed of 3 cels by above-mentioned system by pulling machine
In standby transition coating, soak 30 seconds, application is completed with the speed lifting of 1.0 cels then, is being transferred to rapidly
Under the uviol lamp of 1000 W, irradiate 30 seconds, be placed in after taking-up and hang on clean place, it is to avoid conduit contacts with each other；Then will be complete
Conduit into transition zone application will be immersed in leaching in the lubrication coating of above-mentioned preparation by pulling machine with the speed of 3 cels
Bubble 30 seconds, then with the lifting of the speed of 1.0 cels after, shine being transferred to be provided with the solidification case of 400 W uviol lamps rapidly
Penetrate completion of cure by 150 seconds.
Performance test：
In method shown in embodiment 1, carried out with the speed of 0.5 cel respectively under the g load of 100 g, 300 g, 500 respectively
Reciprocating friction tested for 20 cycles, obtains coefficient of friction and is respectively 0.014,0.020,0.025.
Claims (10)
1. a kind of hydrophilic modifying coating on medical introducing duct surface, it is characterised in that the hydrophilic modifying coating is by transition coating
Constitute with lubrication coating, the composition of transition coating and the parts by weight of each component are：Binding resin 5-10 parts, light
I 0.1-0.2 parts of initiator, levelling agent 0.05-0.1 parts, I 85-95 parts of solvent；The composition and each component of the lubrication coating
Parts by weight be：Hydrophilic resin 5-10 parts, water cross-linking agent 1-5 parts, II 0.2-0.5 parts of light trigger, II 80-95 of solvent
Part.
2. hydrophilic modifying coating as claimed in claim 1, it is characterised in that the binding resin is unsaturated acrylic resin,
One or two mixture in unsaturated polyurethanes acrylate.
3. hydrophilic modifying coating as claimed in claim 1, it is characterised in that the light trigger I is 1- hydroxycyclohexylphenyls
One kind in ketone, 2- hydroxyl -4'- (2- hydroxy ethoxies) -2- methyl phenyl ketones, 2- hydroxy-2-methyl -1- phenyl -1- acetone
Or two kinds of compositionss；The light trigger II is 1- hydroxycyclohexyl phenyl ketones, 2- hydroxyl -4'- (2- hydroxy ethoxies) -2-
One or more mixture in methyl phenyl ketone, 2- hydroxy-2-methyl -1- phenyl -1- acetone, benzophenone.
4. hydrophilic modifying coating as claimed in claim 1, it is characterised in that the levelling agent is the BKY of Bi Ke companies production
333rd, one or two the mixture in the DC57 of Dow Corning Corporation's production.
5. hydrophilic modifying coating as claimed in claim 1, it is characterised in that the solvent I is ethanol, isopropanol, ethyl acetate
In one or two mixture；The solvent II is methanol, ethanol, the two or more mixture in isopropyl alcohol and water.
6. hydrophilic modifying coating as claimed in claim 1, it is characterised in that the hydrophilic resin is Polyethylene Glycol, polyethylene
One kind in alcohol, polyvinylpyrrolidone, hyaluronic acid, NVP-hydroxyethyl methylacrylate copolymer or
Two or more compositionss.
7. hydrophilic modifying coating as claimed in claim 1, it is characterised in that the water cross-linking agent is two propylene of Polyethylene Glycol
Acid esters.
8. as any one of claim 1 to 7 medical introducing duct surface hydrophilic modifying coating, it is characterised in that the painting
The using method of material is：Jing ethanol purges clean conduit is soaked the 10-30 seconds in transition coating, then with 1.0-1.5
The speed lifting of cel completes application, and under the uviol lamp of 1000 W, the irradiation 30-60 seconds obtain final product transition zone；Completed
The conduit for crossing layer application soaks the 10-30 seconds in lubrication coating, after then being lifted with the speed of 0.5-1.0 cels,
The 150-210 seconds are irradiated under the uviol lamp of 400 W can completion of cure.
9. hydrophilic modifying coating as claimed in claim 8, it is characterised in that the material of the conduit is polyurethane, polrvinyl chloride
Or polyester.
10. hydrophilic modifying coating as claimed in claim 8, it is characterised in that it is described catheter surface formed by transition zone and
Lubricating layer formed the lubricity of hydrophilic lubrication layer and the detection method of stability be：Insert a diameter and lead in catheter interior
The steel column of bore formed objects, makes catheter shape keep constant, conduit is horizontally fixed in the tank for filling water, immersion 30
Carried out respectively back and forth with the speed of 0.5 cel with silica gel piece as antithesis in different loads on sound tester for friction between after second
Frictional experiment.
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| CN201611073783.1A CN106540336B (en) | 2016-11-29 | 2016-11-29 | Hydrophilic modified coating on surface of medical interventional catheter |
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| CN201611073783.1A CN106540336B (en) | 2016-11-29 | 2016-11-29 | Hydrophilic modified coating on surface of medical interventional catheter |
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Cited By (8)
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| CN107376029A (en) * | 2017-07-17 | 2017-11-24 | 江西丰临医疗科技股份有限公司 | A kind of medical hydrophilic lubrication coating and its method for coating |
| CN107412883A (en) * | 2017-04-27 | 2017-12-01 | 大连理工大学 | A kind of hydrophilic superslide coating for medical apparatus surface and preparation method thereof |
| CN107868269A (en) * | 2017-12-12 | 2018-04-03 | 湖南平安医械科技有限公司 | A kind of light proofing infusion apparatus catheter surface method of modifying |
| CN109851831A (en) * | 2018-12-27 | 2019-06-07 | 脉通医疗科技(嘉兴)有限公司 | Medical tubing and preparation method thereof |
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| CN115487362A (en) * | 2022-09-21 | 2022-12-20 | 上海康德莱医疗器械股份有限公司 | Ultraviolet curing super-hydrophilic super-lubricating double-layer coating system for catheter and guide wire |
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