CN101812265A - Hydrophilic coat solution applied to surface of medicinal instrument and preparation method thereof - Google Patents
Hydrophilic coat solution applied to surface of medicinal instrument and preparation method thereof Download PDFInfo
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- CN101812265A CN101812265A CN200910067936A CN200910067936A CN101812265A CN 101812265 A CN101812265 A CN 101812265A CN 200910067936 A CN200910067936 A CN 200910067936A CN 200910067936 A CN200910067936 A CN 200910067936A CN 101812265 A CN101812265 A CN 101812265A
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Abstract
The invention discloses hydrophilic coat solution applied to the surface of a medicinal instrument, which comprises modified polyurethane dispersing liquid serving as matrix polymer, hydrophilic polymer and reaction activity crosslinking agent. A preparation method for the hydrophilic coat solution comprises the following steps: (1) dissolving the hydrophilic polymer in water uniformly to form hydrophilic polymer solution, and stirring the solution uniformly; (2) dissolving the matrix polymer in the water uniformly, adding the matrix polymer solution into the hydrophilic polymer solution prepared in the step (1), and stirring the solution uniformly; and (3) adding the reaction activity crosslinking agent into the solution, and stirring the solution uniformly. The aqueous system-based hydrophilic coat solution reduces the used amount of a solvent, and reduces harm to an environment and an operator; the preparation method is simple and easy to operate, and can be applied to the surfaces of multiple medicinal instruments, improve the surface lubricating property of the medicinal instrument, reduce the friction coefficient and improve the effect of lubrication action; and the coating method is a one-step method, avoids processes of plasma pretreatment and the like for materials, is simple and can reduce the cost of the coat.
Description
Technical field
The present invention relates to a kind of hydrophilic coating system and preparation method thereof, especially relate to a kind of hydrophilic coating system that is applied to medical apparatus surface and preparation method thereof, and it is coated to the method for medical apparatus surface.
Background of invention
In medical application fields, in use often there are the big problem of frictional force in undressed medicine equipment such as interposing catheter.Conduit need carry out surface lubrication to it and handle when inserting or extracting tissue, to reduce the painful injury that reaches patient of patient, makes things convenient for the patient to operate simultaneously.Implement coating at medical apparatus surface and become a kind of effective and necessary means.
Medical apparatus surface is carried out modification, the effect that its highly hydrophobic or highly-hydrophilic can be reached reduce frictional coefficient, improve lubrication.Can be if will obtain high hydrophobic coating to surface-coated silicone oil, the contour hydrophobic substance of castor-oil plant oils, but this treatment process effect is relatively poor and firmness is not good.High hydrophilic coating is compared with hydrophobic coating in the past has better oilness and firmness, and the reduction skin friction coefficient can absorb water rapidly behind the chance water.
United States Patent (USP) 5091205 has been announced a kind of method of making hydrophilic coating, this technology is two-step approach, with isocyanic ester as base coat, with polyacrylic acid as the hydrophilic lubrication coating, this method adopts methyl ethyl ketone as solvent, makes coating curing under the condition more than 60 degrees centigrade.The shortcoming of this method is that whole system is a solvent system, and environment and operator are damaged easily, is heating and curing simultaneously to change the character of material easily.
United States Patent (USP) 6169127 has been announced a kind of hydrophilic coating making method based on plasma process, after the substrate passed surface plasma pre-treatment, material surface obtains active group, carry out graft reaction on this basis again, high molecular polymer is grafted to material surface or carries out the monomer initiated polymerization.The shortcoming of this method is for carrying out plasma pretreatment to base material, and apparatus expensive and complex process have increased product cost greatly.
The ideal coating should be water-based system, can avoid the injury of solvent system, simultaneously can be applied to multiple unlike material and do not need material surface carried out pre-treatment measures with high costs such as plasma, corona discharge, glow discharge, high-energy radiation environment and operator.
Summary of the invention
The purpose of this invention is to provide a kind of hydrophilic coating solution that is applied to medical apparatus surface, increase the medical apparatus surface oilness.This coating solution is based on water-based system, has reduced the use of solvent to the full extent, has reduced the injury to environment and operator.
Another object of the present invention provides a kind of preparation method of above-mentioned hydrophilic coating solution.
A further object of the invention provides and a kind of above-mentioned hydrophilic coating solution is coated in the method for medical apparatus surface, and this method does not need material is carried out operations such as plasma pretreatment, and coating method is simple, can reduce the coating cost.
The hydrophilic coating solution that is applied to medical apparatus surface of the present invention, comprising:
A) as the modified polyurethane dispersion liquid of matrix polymer;
B) hydrophilic polymer;
C) reactive behavior linking agent.
In this hydrophilic coating solution, can also comprise other modified additives such as wetting agent or defoamer.
Described hydrophilic polymer is high molecular polymer or the monomer with hydrophilic radical, is selected from Polyvinylpyrolidone (PVP), N-vinyl pyrrolidone, polyoxyethylene glycol, polyacrylic acid, polyacrylamide, POLYPROPYLENE GLYCOL, or polyacrylic acid acrylamide copolymer.The molecular weight of hydrophilic polymer is 4000-5000000, and the content of hydrophilic polymer is 1%-15% (pressing massfraction calculates).
Described matrix polymer is carboxylic modified polyurethane dispersion liquid, and its content is 1%-20% (pressing massfraction calculates).Polyurethane dispersing liquid to the material bonding firmly also has excellent biological compatibility simultaneously, and carboxylic modified polyurethane dispersion liquid is all right crosslinking curing under the linking agent effect, further improves its firmness and chemical resistant properties.
Described reactive behavior linking agent is an epoxy silane coupling agent, and its content is 0.005-5% (pressing massfraction calculates).The epoxide group of an end can react with the carboxyl in the polyurethane dispersing liquid in the epoxy silane linking agent, and polycondensation takes place for self after the alkoxysilane groups hydrolysis of the other end.
Described wetting agent is selected from the polyether-modified polysiloxane of end group, high molecular organosilicon or fluorocarbon.Its content is 0.001%-1% (pressing massfraction calculates).Wetting agent can reduce the surface tension of water-based system, improves the sticking power of coating to base material.Defoamer is polydimethylsiloxane or polyether-modified silicon, and its content is 0.001%-1% (pressing massfraction calculates).Add defoamer and can reduce foam at short notice, and can suppress the generation of bubble.
Under the situation that has linking agent to exist, the polyurethane dispersing liquid crosslinking curing, hydrophilic polymer forms half interpenetrating network structure with cross-linked polyurethane at coated body surface, and the coating firmness is further strengthened.
The hydrophilic coating system of stating that is applied to medical apparatus surface, wherein said medical apparatus surface can be metallic surface or frosting.Described metal can be a stainless steel; Described plastics can be a kind of in polyvinyl chloride, urethane, polymeric amide, nylon, polyethylene, polypropylene, polycarbonate, polystyrene, silica gel or the natural rubber.
The preparation method of this hydrophilic coating solution may further comprise the steps: (1) dissolves the uniform preparation water polymer solution of getting married with hydrophilic polymer in water, stir; (2) matrix polymer is dissolved in water evenly, add ready-formed hydrophilic polymer solution in the step (1), stir; (3) add the reactive behavior linking agent, stir.In preparation process, visual particular case adds other modified additives such as wetting agent or defoamer, for example, improve coating and adhere to situation on medical apparatus surface, can add an amount of wetting agent; Perhaps in preparation process if too much bubble can add proper quantity of defoaming agent.
This hydrophilic coating solution can be applied to medical apparatus surface, improves the medical apparatus surface oilness, reduces the effect of frictional coefficient, raising lubrication.Described medicine equipment can be catheter, interposing catheter, drainage tube, sacculus dilating catheter etc.Described hydrophilic coating solution is coated in the method for medical apparatus surface, is that prepared hydrophilic coating solution is coated in medical apparatus surface, dry then, and surperficial thorough drying is solidified.Coating method can adopt spraying, smear or mode such as dip-coating.Drying conditions is looked coated object and is come surely, and drying at room temperature is optimal condition, when needs shorten time of drying, can take mode such as heating, drying to accelerate the coating curing process.The thickness range of the hydrophilic coating that obtains behind the dry solidification is 0.1 micron to 100 microns.Coat-thickness is thick more, and oilness is good more, but firmness will reduce accordingly, and usually, 1 micron to 10 microns is the ideal coat-thickness.
Hydrophilic coating solution of the present invention is based on water-based system, reduced the use of solvent to the full extent, reduced injury to environment and operator, its preparation method is simple, easy to operate, can be applied to the various medical devices surface, improve the medical apparatus surface oilness, reduce the effect of frictional coefficient, raising lubrication, and the method that above-mentioned hydrophilic coating solution is coated in medical apparatus surface is a single stage method, do not need material is carried out operations such as plasma pretreatment, coating method is simple, can reduce the coating cost.
Embodiment
Below by specific embodiment the present invention is further specified.
Embodiment 1
20 gram Polyvinylpyrolidone (PVP) powder (K90 level) fully are dissolved in the 80 gram water, and stirring obtains polymers soln 1.
(R986 DSM) is dissolved in the 80 gram deionized waters, adds 5 gram polymers solns 1, and the back that stirs adds 0.15 gram epoxy silane linking agent, continues to stir 20 minutes with 2.5 gram polyurethane dispersing liquids.
In above-mentioned solution, add 0.03 gram polyether-modified polysiloxane base material wetting agent (Wet 245, Degussa), continue to stir 1 hour.This coating system can keep satisfactory stability in a long time.
Embodiment 2
20 gram Polyvinylpyrolidone (PVP) powder (K90 level) fully are dissolved in the 80 gram water, and stirring obtains polymers soln 1.
(R986 DSM) is dissolved in the 80 gram deionized waters, adds 15 gram polymers solns 1, and the back that stirs adds 0.6 gram epoxy silane linking agent, continues to stir 20 minutes with 20 gram polyurethane dispersing liquids.
In above-mentioned solution, add the polyether-modified silicon defoaming agent of 0.1 gram medical grade, continue to stir 20 minutes.This coating system can keep satisfactory stability in a long time.
Embodiment 3
20 gram Polyvinylpyrolidone (PVP) powder (K90 level) fully are dissolved in the 80 gram water, and stirring obtains polymers soln 1.
(R986 DSM) is dissolved in the 70 gram deionized waters, adds 25 gram polymers solns 1, and the back that stirs adds 0.8 gram epoxy silane linking agent, continues to stir 20 minutes with 20 gram polyurethane dispersing liquids.
Embodiment 4
5 gram polyoxyethylene glycol (medical grade PEG8000, Dow Chemical) powder fully are dissolved in the 100 gram water, and stirring obtains polymers soln 1.
(R986 DSM) is dissolved in the 50 gram deionized waters, adds 30 gram polymers solns 1, and the back that stirs adds 0.3 gram epoxy silane linking agent, continues to stir 20 minutes with 10 gram polyurethane dispersing liquids.
Embodiment 5
20 gram Polyvinylpyrolidone (PVP) powder (K90 level) fully are dissolved in the 80 gram water, and stirring obtains polymers soln 1.
(R986 DSM) is dissolved in the 80 gram deionized waters, adds 10 gram polymers solns 1, and the back that stirs adds 0.14 gram epoxy silane linking agent, continues to stir 20 minutes with 10 gram polyurethane dispersing liquids.
In above-mentioned solution, add 0.03 gram polyether-modified polysiloxane base material wetting agent (Wet 245, Degussa), continue to stir 10 minutes.The polymeric amide foley's tube is immersed in this prescription conduit at room temperature dry 24 hours.Catheter surface is as good as during with coating not under dry state, becomes sliding immediately after meeting water.
Embodiment 6
20 gram Polyvinylpyrolidone (PVP) powder (K90 level) fully are dissolved in the 80 gram water, and stirring obtains polymers soln 1.
(R972 DSM) is dissolved in the 78 gram deionized waters, adds 10 gram polymers solns 1, and the back that stirs adds 0.11 gram epoxy silane linking agent, continues to stir 20 minutes with 12 gram polyurethane dispersing liquids.
316L stainless steel seal wire is immersed in this prescription, and seal wire goes to after at room temperature dry 2 hours and continued in 80 ℃ of baking ovens dry 4 hours.Seal wire after the coating is as good as during with coating not under dry state, becomes sliding immediately after meeting water.
Claims (14)
1. hydrophilic coating solution that is applied to medical apparatus surface, comprising:
A) as the modified polyurethane dispersion liquid of matrix polymer;
B) hydrophilic polymer;
C) reactive behavior linking agent.
2. the described hydrophilic coating solution that is applied to medical apparatus surface of claim 1 wherein also comprises other modified additives such as wetting agent or defoamer.
3. the described hydrophilic coating solution that is applied to medical apparatus surface of claim 1, wherein said hydrophilic polymer is high molecular polymer or the monomer with hydrophilic radical, be selected from Polyvinylpyrolidone (PVP), the N-vinyl pyrrolidone, polyoxyethylene glycol, polyacrylic acid, polyacrylamide, POLYPROPYLENE GLYCOL, or polyacrylic acid acrylamide copolymer.
4. the described hydrophilic coating solution that is applied to medical apparatus surface of claim 3, the molecular weight of wherein said hydrophilic polymer is 4000-5000000.
5. the described hydrophilic coating solution that is applied to medical apparatus surface of claim 1, wherein said modified polyurethane dispersion liquid is carboxylic modified polyurethane dispersion liquid.
6. the described hydrophilic coating solution that is applied to medical apparatus surface of claim 1, wherein said reactive behavior linking agent is an epoxy silane coupling agent.
7. the described hydrophilic coating solution that is applied to medical apparatus surface of claim 2, wherein said wetting agent is selected from the polyether-modified polysiloxane of end group, high molecular organosilicon or fluorocarbon.
8. the described hydrophilic coating solution that is applied to medical apparatus surface of claim 2, wherein said defoamer is selected from polydimethylsiloxane or polyether-modified silicon.
9. the described hydrophilic coating solution that is applied to medical apparatus surface of claim 1, wherein said modified polyurethane dispersion liquid content is 1%-20% (pressing massfraction calculates), the content of described hydrophilic polymer is 1-15% (pressing massfraction calculates), and the content of described reactive behavior linking agent is 0.005-5% (pressing massfraction calculates).
10. the described hydrophilic coating solution that is applied to medical apparatus surface of claim 2, wherein the content of stating wetting agent is 0.001%-1% (pressing massfraction calculates), the content of described defoamer is 0.001%-1% (press massfraction calculating).
11. the described hydrophilic coating system that is applied to medical apparatus surface of claim 1, wherein said medical apparatus surface can be metallic surface or frosting.
12. the described hydrophilic coating solution that is applied to medical apparatus surface of claim 11, wherein said metal can be a stainless steel; Described plastics can be a kind of in polyvinyl chloride, urethane, polymeric amide, nylon, polyethylene, polypropylene, polycarbonate, polystyrene, silica gel or the natural rubber.
13. the described preparation method who is applied to the hydrophilic coating solution of medical apparatus surface of claim 1 may further comprise the steps:
(1) hydrophilic polymer is dissolved the uniform preparation water polymer solution of getting married in water, stir; (2) matrix polymer is dissolved in water evenly, add ready-formed hydrophilic polymer solution in the step (1), stir; (3) add the reactive behavior linking agent, stir.
14. one kind is coated in the method for medical apparatus surface with hydrophilic coating solution, this method is that each the described hydrophilic coating solution among the claim 1-10 is coated in medical apparatus surface, and is dry then, and surperficial thorough drying is solidified.
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