CN102993407B - Water-based ultraviolet curing resin, coating based on water-based ultraviolet curing resin and medical catheter - Google Patents
Water-based ultraviolet curing resin, coating based on water-based ultraviolet curing resin and medical catheter Download PDFInfo
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Abstract
The invention discloses water-based ultraviolet curing resin, coating based on the water-based ultraviolet curing resin and a medical catheter. The water-based ultraviolet curing resin is high in tensile strength, capable of being firmly attached to polyurethane high polymer materials and good in biocompatibility. When hydrophilic lubricating coating is irradiated by ultraviolet, a urethane acrylate photoactivity low polymer, N-vinyl pyrrolidone and vinyl silicone perform free radical copolymerization reaction and perform graft polymerization with the catheter and guide wire surface which are irradiated by the ultraviolet to form a polyurethane-polyvinyl pyrrolidone (PVP)-organosilicon high-molecular polymer film. The bonding force between a film forming matter and polyurethane catheter materials is good, and the film forming matter is not liable to drop off. The coating is free of toxicity and good in biocompatibility. When the coating is in the environment having water, such as contacting with liquid, the surface of the coating quickly absorbs water to form a hydration layer, frictional resistance generated in the moving process of machines can be remarkably reduced, and the hydrophilic lubricating coating does not drop off when pipe inserting is performed.
Description
Technical field
The present invention relates to a kind of novel water base UV cured resin, and use the composite hydrophilic lubrication coating obtaining of this resin, so that the medical catheter preparing.
Background technology
Intervention diagnosis and therapy technology is under the guiding of the image documentation equipments such as x-ray, CT and M R (nucleus magnetic resonance), utilize the apparatuses such as specific puncture needle, seal wire or conduit, need not open tissue and can accurately arrive the medical science new technology that diseased region is diagnosed and treated.Because intervention apparatus is when entering or extracting human body and moving, all need to have the surface of oilness, to avoid damaging in-vivo tissue in human body.
With regard to general material, use Precision Method processing to obtain smooth surface, but can find that by scanning electron microscope analysis its surface still has many projections, these projections not only make its surfaceness increase, and tend to activate thrombin, cause thrombus to generate, or because of moving the very large resistance of experience in human body natural cavity organization, cause the interruption of interventional programs, be difficult to meet service requirements.
Polymer materials is easy to carry out modification or grafting is processed, and by surface treatment, can improve its surface property, improves oilness and the biocompatibility of material, and therefore, polymer materials is more and more applied to manufacturing interventional medical apparatus.Polyurethane material smooth surface and good biocompatibility, monomer ratio during with polymerization, kind difference and product is different, its kindliness and hardness also differ widely, and are a kind of high-performance, easily the macromolecular material of modification, has been widely used in manufacturing the medicine equipment using in intervention diagnosis and therapy.Present stage, for the manufacture of medicine equipment urethane used be a kind of polyether-type polyurethane(s), recently developed again the urethane that is separated (SPU).
Although the medicine equipment that uses polyurethane material manufacture to obtain has good characteristic, its surface lubrication is Shortcomings still, and the adsorptivity of thrombocyte and protein is still existed, and needs further to be improved.By polyurethane material being carried out to surface modification treatment to improve its performance, it is more common a kind of scheme.
As people such as Wu Zengyong, to adopt urethane (PUR)/polyvinylpyrrolidone (PVP) interpenetrating network system to carry out PUR material surface coating modified, the impact of the PVP that has studied different content on performances such as coatingsurface pattern, water-absorbent, oilness, stabilityes.Result shows: after modification, the lubricity of material surface obviously improves, and when PVP massfraction is 2.5%, frictional coefficient 0.45 before by modification drops to 0.074; Coating stability is better.The people such as Luo Xianglin with UV-light directly cause hydrophilic monomer N-V-Pyrol RC (NVP), acrylamide carries out graft reaction on medical polyurethane (PU) surface, can improve the oilness on PU surface.Study the factor that affects grafting density, frictional coefficient, measured per surface area water-intake rate, water contact angle.Its experimental result shows: graft polymerization reaction can make medical PU surface formation hydrophilic surface layer, frictional coefficient be down to below 0.1 by 0.6.
Material is carried out to surface-treated simultaneously, and the new problem of also bringing, as the sticking power of coating is not high, is easy to come off, and this has also limited its application and popularization.In China, high-end interventional medical apparatus is commonly Overseas Company, and as monopolizations such as Japanese Terumo Corp, price is high.Meanwhile, existing method of modifying is comparatively complicated, and production cost is higher.
Develop a kind of novel being necessary for medical apparatus surface is material modified.
Summary of the invention
One object of the present invention is to provide a kind of water base UV cured resin.
Another object of the present invention is to provide a kind of hydrophilic lubrication coating based on above-mentioned water base UV cured resin.
A further object of the present invention is to provide a kind of medical catheter of self lubricity.
The technical solution used in the present invention is:
A water base UV cured resin, its preparation method is as follows:
1) polycaprolactone glycol is dried to water content not higher than 0.05%, temperature adjustment to 30～70 ℃;
2) under the protection of protection gas, add diphenylmethanediisocyanate, polyreaction;
3) be warming up to 70～80 ℃, add dihydroxymethyl acid, continue reaction, obtain base polyurethane prepolymer for use as A;
4) in base polyurethane prepolymer for use as A, add organic solvent, regulate its viscosity, drip the acrylate monomer of hydroxyl at 60～70 ℃, after completion of the reaction, obtain urethane acrylate multipolymer;
5) at urethane acrylate multipolymer, add neutralizing agent to neutralize remaining carboxyl completely, add water-dispersion and remove residual organic solvent, obtain water base UV cured resin;
Wherein,
The NCO base of diphenylmethanediisocyanate: both OH bases of polycaprolactone glycol and dihydroxymethyl acid and mol ratio be (1.3～1.8): 1;
The usage quantity of dihydroxymethyl acid is 4.0～8.0% of polycaprolactone glycol and diphenylmethanediisocyanate total mass;
The usage quantity of the acrylate monomer of hydroxyl is 10.0～25.0% of polycaprolactone glycol and diphenylmethanediisocyanate total mass.
As a further improvement on the present invention, the molecular weight of polycaprolactone glycol is 500～2000.
As a further improvement on the present invention, dihydroxymethyl acid is selected from dimethylol propionic acid and dimethylolpropionic acid.
As a further improvement on the present invention, the acrylate monomer of hydroxyl is selected from Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate and Rocryl 410.
As a further improvement on the present invention, the time of polycaprolactone glycol and diphenylmethanediisocyanate polyreaction is 1.5～2.5h.
As a further improvement on the present invention, add after dihydroxymethyl acid, continue reaction 1.5h～2h.
As a further improvement on the present invention, total time for adding of the acrylate monomer of hydroxyl is controlled at 50～60min.
UV solidifies a hydrophilic lubrication coating, and its ratio of quality and the number of copies is as follows:
10～50 parts of water base UV cured resins;
20～50 parts of NVPs;
0.5～3 part of vinyl silanes;
And appropriate light trigger, defoamer, flow agent, and use aqueous solvent to regulate its viscosity;
Wherein, water base UV cured resin is as described in above-mentioned any one.
As a further improvement on the present invention, vinyl silanes is selected from vinyl trimethylsilane and vinyltrimethoxy silane.
A medical catheter, catheter surface is solidified with above-mentioned UV and solidifies hydrophilic lubrication coating.
The invention has the beneficial effects as follows:
Water base UV cured resin of the present invention has high tensile, can be attached to securely on polyurethane high molecule material, meanwhile, has biocompatibility well.
Hydrophilic lubrication coating of the present invention, after UV-irradiation, to there is free radicals copolymerization reaction in urethane acrylate photolytic activity oligopolymer, NVP, vinyl organosilicon, and there is graft polymerization with conduit, seal wire surface through UV-irradiation, form the organosilyl polymer membrane of urethane-PVP-, this film forming matter and polyurethane guide tube material bonding force are good, difficult drop-off.Coating is nontoxic, has good biocompatibility.Once in aqueous environment, after contact body fluid, the coatingsurface formation hydration layer that absorbs water rapidly, significantly reduce the friction resistance of apparatus in moving process, and wetting ability slip coating does not come off when intubate.
Medical catheter of the present invention, be easy to preparation, after meeting water, its surface can form the hydration layer with oilness, its frictional coefficient is lower than 0.1, there is lasting oilness, can significantly reduce its frictional force, simultaneously, the existence of hydration layer also can significantly reduce the adhesion of the body intravascular coagulation factor, greatly reduces thrombotic possibility.
Embodiment
A water base UV cured resin, its preparation method is as follows:
1) polycaprolactone glycol is dried to water content not higher than 0.05%, temperature adjustment to 30～70 ℃;
2) under the protection of protection gas, add diphenylmethanediisocyanate, polyreaction;
3) be warming up to 70～80 ℃, add dihydroxymethyl acid, continue reaction, obtain base polyurethane prepolymer for use as A;
4) in base polyurethane prepolymer for use as A, add organic solvent, regulate its viscosity, drip the acrylate monomer of hydroxyl at 60～70 ℃, after completion of the reaction, obtain urethane acrylate multipolymer;
5) at urethane acrylate multipolymer, add neutralizing agent to neutralize remaining carboxyl completely, add water-dispersion and remove residual organic solvent, obtain water base UV cured resin;
Wherein,
The NCO base of diphenylmethanediisocyanate: both OH bases of polycaprolactone glycol and dihydroxymethyl acid and mol ratio be (1.3～1.8): 1;
The usage quantity of dihydroxymethyl acid is 4.0～8.0% of polycaprolactone glycol and diphenylmethanediisocyanate total mass;
The usage quantity of the acrylate monomer of hydroxyl is 10.0～25.0% of polycaprolactone glycol and diphenylmethanediisocyanate total mass.
In aforesaid method, OH base in polycaprolactone glycol PCL and the NCO radical reaction of diphenylmethanediisocyanate MDI, generate base polyurethane prepolymer for use as, adds afterwards dihydroxymethyl acid to carry out modification, the further modification of acrylate monomer that adds afterwards hydroxyl, obtains UV cured resin.For regulating the organic solvent of base polyurethane prepolymer for use as A viscosity can conventional organic solvent, preferably those are harmless to human body basic, with water compatible again not can with the organic solvent of isocyanate reaction, as acetone, butanone, ethyl acetate, DMF, its add-on is preferably 5～15% of polycaprolactone glycol, diphenylmethanediisocyanate and dihydroxymethyl acid total mass.
As a further improvement on the present invention, the molecular weight of polycaprolactone glycol is 500～2000.
As a further improvement on the present invention, dihydroxymethyl acid is selected from dimethylol propionic acid and dimethylolpropionic acid.
As a further improvement on the present invention, the acrylate monomer of hydroxyl is selected from Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate and Rocryl 410.
As a further improvement on the present invention, the time of polycaprolactone glycol and diphenylmethanediisocyanate polyreaction is 1.5～2.5h.
As a further improvement on the present invention, add after dihydroxymethyl acid, continue reaction 1.5h～2h.
As a further improvement on the present invention, total time for adding of the acrylate monomer of hydroxyl is controlled at 50～60min so that reaction can be more evenly, carry out stably.
UV solidifies a hydrophilic lubrication coating, and its ratio of quality and the number of copies is as follows:
10～50 parts of water base UV cured resins;
20～50 parts of NVPs;
0.5～3 part of vinyl silanes;
And appropriate light trigger, defoamer, flow agent, and use aqueous solvent to regulate its viscosity;
Wherein, water base UV cured resin is as described in above-mentioned any one.
For the aqueous solvent of adjusting coating viscosity, can be the mixing solutions of lower alcohol and water, in assurance coating without harmful composition, lower alcohol is preferably the alcohol of C2～C4.The example of these lower alcohols has ethanol, propyl alcohol, Virahol etc.
As a further improvement on the present invention, vinyl silanes is selected from vinyl trimethylsilane and vinyltrimethoxy silane.
A medical catheter, catheter surface is solidified with above-mentioned UV and solidifies hydrophilic lubrication coating.
The application of coating can be adopted with the following method:
1) by polyurethane base material surface scrub, under ultraviolet light, irradiate certain hour;
2) base material is immersed to water-based ultraviolet (UV) curable coating, stop certain hour, make its surface coating paint;
3) take out base material, be placed in air to its surface drying;
4) use UV-irradiation coating, make coating completely curing.
Concrete application is as follows:
Wipes of alcohol wash clean is used in polyurethane base material surface, put into 2 mw/ cm
2ultraviolet light under irradiate 2 minutes, then with 2cm/ speed second, immerse water-based ultraviolet (UV) curable coating, stop 5 seconds, with 0.5cm/ speed second, take out again, in air drying after 10 minutes, through UV-irradiation 1～10 minute, more excellent 3～6 minutes, ultraviolet ray intensity was 1mW/cm
2～10W/ cm
2, more excellent 1.5～3mw/ cm
2, obtain solidified coating.
Using neutralizing agent by carboxyl neutralization residual in UV cured resin, is in order to make the aqueous dispersions integral body of resin be neutral or alkalescence on the weak side, to avoid NVP in coating process to be hydrolyzed to acetaldehyde and pyrrolidone.For achieving the above object, by regulating the amount of neutralizing agent, by pH regulator to 7.0～7.5 of UV resin aqueous dispersions.The example of the neutralizing agent that this area is common has triethylamine, also can use other neutralizing agent neutralization.
While mixing in order to reduce, produce too much foam, affect the performance of coating, in the mixing process of coating, can add appropriate defoamer, generally speaking, the consumption of defoamer is 0.1～1.0% of body material (water base UV cured resin, NVP and vinyl silanes) total mass.Under at subnormal ambient, mix, or be placed under condition of negative pressure and carry out defoaming treatment after conventional mixing, can further reduce the consumption of defoamer, even without adding defoamer.Because the singularity of application of paints occasion, defoamer is harmless defoamer preferably, and as silicone antifoam agent, the example of this defoamer has the German Bi Ke BYK020 of company, Degussa company's T EGO825 etc.
In order to improve the levelling property of coating, can in coating, add flow agent, the example of flow agent has the German Bi Ke BYK333 of company, Degussa company's T EGO410 etc.
Below in conjunction with embodiment, further illustrate the present invention.
In following examples:
The polycaprolactone glycol using is all predrying is less than 0.05% to biodiversity relative content, and its manufacturer is Japanese Daisel chemical industry Co., Ltd;
After solidifying, the frictional coefficient of coating in water adopts static friction coefficient tester (GT-7012-HG type, High Speed Rail Testing Instruments company limited) to measure;
Press the adhere firmly degree of GB/T 13217.7-2009 mensuration coating.
embodiment 1
1, synthetic water base UV cured resin
1) take the polycaprolactone glycol that 100 grams average molecular weights are 500 (about the 0.2mol altogether) (trade mark: PCLL205AL); be warming up to 30 ℃; at nitrogen atmosphere protection and under stirring, add 100.4 grams of diphenylmethanediisocyanate MDI(about 0.40mol altogether) reaction 2.5h
2) be warming up to 70～80 ℃, then add 16.0 grams of dimethylolpropionic acid DM
ba(is about 0.11mol altogether), reaction 2h, obtains base polyurethane prepolymer for use as A;
3) in base polyurethane prepolymer for use as A, add 23 grams of acetone viscosity reductions, then drip 21.6 grams of acrylate hydroxyl ethyl ester monomers, temperature of reaction is controlled at 65 ℃, at 55 minutes, drips off;
4) cool the temperature to room temperature, obtain urethane acrylate multipolymer;
5) under stirring at room, in above-mentioned multipolymer, add 11.1 grams of triethylamines and 525 grams of water to carry out salt-forming reaction, after reacting completely, under vigorous stirring, add water-dispersion, then decompression steams acetone, obtains the solution of UV solidfication water polyurethane acrylate oligopolymer, obtains water base UV cured resin, its pH value is 7.3, and solid content is 31.8%.
2, preparation wetting ability slip coating
In the container stirring at band, take 35 grams of above-mentioned water base UV cured resins, 25 grams of NVPs, start stirring, under agitation, add 0.1 gram of defoamer BYK020,0.2 gram of flow agent BYK333,0.5 gram of vinyl trimethylsilane, 18 grams of ethanol and 19.2 grams of deionized waters, finally add 2 grams of light trigger alpha-hydroxyacetophenones, after stirring, make water-based ultraviolet (UV) curable wetting ability slip coating.
At 25 ℃, with being coated with 4 glasss of viscosity of measuring this coating, it is 18 seconds.
3, the application of coating and curing
Choose the TPU58680 polyurethane base material that U.S.'s Noveon Asia-Pacific company limited produces, then wipes of alcohol wash clean is used in its surface, put into 2 mw/ cm
2ultraviolet light under irradiate 2 minutes, then with 2cm/ speed second, immerse water-based ultraviolet (UV) curable coating, stops 5 seconds, then with the taking-up of 0.5cm/ speed second, in air drying after 10 minutes, through UV-irradiation 5 minutes, ultraviolet ray intensity was 2mw/ cm
2, finally at TPU surface cure, obtain coating.
After testing, the frictional coefficient of coating in water is 0.09, has Hydrophilic lubrication; Attachment fastness 100%, film does not come off, and wear resistance is good.
embodiment 2
1, synthetic water base UV cured resin
1) take the polycaprolactone glycol that 100 grams average molecular weights are 850 (about the 0.12mol altogether) (trade mark: PCL308), be warming up to 45 ℃, at nitrogen atmosphere protection and under stirring, add 98.2 grams of diphenylmethanediisocyanate MDI(about 0.39mol altogether) reaction 2.5 h;
2) be warming up to 70～80 ℃, then add 14.9 grams of dimethylolpropionic acid DMBA(about 0.10mol altogether), reaction 2h, obtains base polyurethane prepolymer for use as A;
3) in base polyurethane prepolymer for use as A, add 12.5 grams of acetone viscosity reductions, then drip 49.5 grams of acrylate hydroxypropyl acrylate monomers, temperature of reaction is controlled at 65 ℃, at 55 minutes, drips off;
4) cool the temperature to room temperature, obtain urethane acrylate multipolymer;
5) under stirring at room, in above-mentioned multipolymer, add 11.1 grams of triethylamines and 432 grams of water to carry out salt-forming reaction, after reacting completely, under vigorous stirring, add water-dispersion, then decompression steams acetone, obtains the solution of UV solidfication water polyurethane acrylate oligopolymer, obtains water base UV cured resin, its pH value is 7.1, and solid content is 31.0%.
2, preparation wetting ability slip coating
In the container stirring at band, take 38 grams of above-mentioned water base UV cured resins, 50 grams of NVPs, start stirring, under agitation, add 0.5 gram of BYK020 defoamer, 0.2 gram of BYK333 flow agent, 1.5 grams of vinyl trimethylsilane, 15 grams of Virahols and, 14.8 grams of deionized waters, finally add 1.5 gram 2,2-dimethyl-2-hydroxy acetophenone, after stirring, makes water-based ultraviolet (UV) curable wetting ability slip coating.
At 25 ℃, with being coated with 4 glasss of viscosity of measuring this coating, it is 19 seconds.
Choose the TPU58680 polyurethane base material that U.S.'s Noveon Asia-Pacific company limited produces, then wipes of alcohol wash clean is used in its surface, put into 2 mw/ cm
2ultraviolet light under irradiate 2 minutes, then with 2cm/ speed second, immerse water-based ultraviolet (UV) curable coating, stops 5 seconds, then with the taking-up of 0.5cm/ speed second, in air drying after 10 minutes, through UV-irradiation 5 minutes, ultraviolet ray intensity was 2mw/ cm
2, finally at TPU surface cure, obtain coating.
After testing, the frictional coefficient of coating in water is 0.08, has Hydrophilic lubrication; Attachment fastness 100%, film does not come off, and wear resistance is good.
embodiment 3
1, synthetic water base UV cured resin
1) take the polycaprolactone glycol that 100 grams average molecular weights are 1000 (about the 0.1mol altogether) (trade mark: PCL210N), be warming up to 60 ℃, at nitrogen atmosphere protection and under stirring, add 64.6 grams of diphenylmethanediisocyanate MDI(about 0.26mol altogether) reaction 1.5 h;
2) be warming up to 70～80 ℃, then add 8.23 grams of dimethylol propionic acid DMPA(about 0.06mol altogether), reaction 1.5 h, obtain base polyurethane prepolymer for use as A;
3) in base polyurethane prepolymer for use as A, add 18.9 grams of DMF viscosity reductions, then drip 24.7 grams of methacrylic ester hydroxyl ethyl ester monomers, temperature of reaction is controlled at 65 ℃, at 50 minutes, drips off;
4) cool the temperature to room temperature, obtain urethane acrylate multipolymer;
5) under stirring at room, in above-mentioned multipolymer, add 6.27 grams of triethylamines and 333 grams of water to carry out salt-forming reaction, after reacting completely, under vigorous stirring, add water-dispersion, then decompression steams acetone, obtains the solution of UV solidfication water polyurethane acrylate oligopolymer, obtains water base UV cured resin, its pH value is 7.5, and solid content is 33.7%.
2, preparation wetting ability slip coating
In the container stirring at band, take 10 grams of above-mentioned water base UV cured resins, 20 grams of NVPs, start stirring, under agitation, add 0.3 gram of TEGO825 defoamer, 0.2 gram of TEGO410 flow agent, 0.5 gram of vinyl trimethylsilane, 12 grams of ethanol and, 18.7 grams of deionized waters, finally add 1.0 grams of α-UVINUL MS 40-sodium sulfonates, after stirring, make water-based ultraviolet (UV) curable wetting ability slip coating.
At 25 ℃, with being coated with 4 glasss of viscosity of measuring this coating, it is 16 seconds.
Choose the TPU58680 polyurethane base material that U.S.'s Noveon Asia-Pacific company limited produces, then wipes of alcohol wash clean is used in its surface, put into 2 mw/ cm
2ultraviolet light under irradiate 2 minutes, then with 2cm/ speed second, immerse water-based ultraviolet (UV) curable coating, stops 5 seconds, then with the taking-up of 0.5cm/ speed second, in air drying after 10 minutes, through UV-irradiation 5 minutes, ultraviolet ray intensity was 2mw/ cm
2, finally at TPU surface cure, obtain coating.
After testing, the frictional coefficient of coating in water is 0.10, has Hydrophilic lubrication; Attachment fastness 100%, film does not come off, and wear resistance is good.
embodiment 4
1, synthetic water base UV cured resin
1) take the polycaprolactone glycol that 100 grams average molecular weights are 2000 (approximately 0.05 the mol altogether) (trade mark: PCL220N), be warming up to 70 ℃, at nitrogen atmosphere protection and under stirring, add 42.2 grams of diphenylmethanediisocyanate MDI(approximately 0.17 mol altogether) reaction 2 h;
2) be warming up to 70～80 ℃, then add 5.86 grams of dimethylol propionic acid DMPA, reaction 1.5h, obtains base polyurethane prepolymer for use as A;
3) in base polyurethane prepolymer for use as A, add 16 grams of ethyl acetate viscosity reductions, then drip 19.5 grams of methacrylic ester hydroxypropyl acrylate monomers, temperature of reaction is controlled at 70 ℃, at 60 minutes, drips off;
4) cool the temperature to room temperature, obtain urethane acrylate multipolymer;
5) under stirring at room, in above-mentioned multipolymer, add 4.45 grams of triethylamines and 555 grams of water to carry out salt-forming reaction, after reacting completely, under vigorous stirring, add water-dispersion, then decompression steams acetone, obtains the solution of UV solidfication water polyurethane acrylate oligopolymer, obtains water base UV cured resin, its pH value is 7.6, and solid content is 32.4%.
2, preparation wetting ability slip coating
In the container stirring at band, take 50 grams of above-mentioned water base UV cured resins, 40 grams of NVPs, start stirring, under agitation, add 0.08 gram of TEGO825 defoamer, 0.20 gram of TEGO410 flow agent, 3.0 grams of vinyltrimethoxy silanes, 25.0 grams of ethanol and, 15.9 grams of deionized waters, finally add 2.5 grams of α-UVINUL MS 40-sodium sulfonates, after stirring, make water-based ultraviolet (UV) curable wetting ability slip coating.
At 25 ℃, with being coated with 4 glasss of viscosity of measuring this coating, it is 19 seconds.
Choose the TPU58680 polyurethane base material that U.S.'s Noveon Asia-Pacific company limited produces, then wipes of alcohol wash clean is used in its surface, put into 2 mw/ cm
2ultraviolet light under irradiate 2 minutes, then with 2cm/ speed second, immerse water-based ultraviolet (UV) curable coating, stops 5 seconds, then with the taking-up of 0.5cm/ speed second, in air drying after 10 minutes, through UV-irradiation 5 minutes, ultraviolet ray intensity was 2mw/ cm
2, finally at TPU surface cure, obtain coating.
After testing, the frictional coefficient of coating in water is 0.08, has Hydrophilic lubrication; Attachment fastness 100%, film does not come off, and wear resistance is good.
Claims (8)
1. a water base UV cured resin, its preparation method is as follows:
1) polycaprolactone glycol is dried to water content not higher than 0.05%, temperature adjustment to 30～70 ℃;
2) under the protection of protection gas, add diphenylmethanediisocyanate, polyreaction;
3) be warming up to 70～80 ℃, add dihydroxymethyl acid, continue reaction, obtain base polyurethane prepolymer for use as A;
4) in base polyurethane prepolymer for use as A, add organic solvent, regulate its viscosity, drip the acrylate monomer of hydroxyl at 60～70 ℃, after completion of the reaction, obtain urethane acrylate multipolymer;
5) at urethane acrylate multipolymer, add neutralizing agent to neutralize remaining carboxyl completely, add water-dispersion and remove residual organic solvent, obtain water base UV cured resin;
Wherein,
The NCO base of diphenylmethanediisocyanate: both OH bases of polycaprolactone glycol and dihydroxymethyl acid and mol ratio be (1.3～1.8): 1;
The usage quantity of dihydroxymethyl acid is 4.0～8.0% of polycaprolactone glycol and diphenylmethanediisocyanate total mass;
The usage quantity of the acrylate monomer of hydroxyl is 10.0～25.0% of polycaprolactone glycol and diphenylmethanediisocyanate total mass;
Dihydroxymethyl acid is selected from dimethylol propionic acid and dimethylolpropionic acid;
The acrylate monomer of hydroxyl is selected from Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate and Rocryl 410.
2. water base UV cured resin according to claim 1, is characterized in that: the molecular weight of polycaprolactone glycol is 500～2000.
3. water base UV cured resin according to claim 1 and 2, is characterized in that: the time of polycaprolactone glycol and diphenylmethanediisocyanate polyreaction is 1.5～2.5h.
4. water base UV cured resin according to claim 1 and 2, is characterized in that: add after dihydroxymethyl acid, continue reaction 1.5h～2h.
5. water base UV cured resin according to claim 1 and 2, is characterized in that: total time for adding of the acrylate monomer of hydroxyl is controlled at 50～60min.
6. UV solidifies a hydrophilic lubrication coating, and its ratio of quality and the number of copies is as follows:
10～50 parts of water base UV cured resins;
20～50 parts of NVPs;
0.5～3 part of vinyl silanes;
And appropriate light trigger, defoamer, flow agent, and use aqueous solvent to regulate its viscosity;
Wherein, water base UV cured resin is as described in claim 1～5 any one.
7. UV according to claim 6 solidifies hydrophilic lubrication coating, it is characterized in that: vinyl silanes is selected from vinyl trimethylsilane and vinyltrimethoxy silane.
8. a medical catheter, is characterized in that: the UV that described catheter surface is solidified with described in claim 6 or 7 solidifies hydrophilic lubrication coating.
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| CN201210582216.4A CN102993407B (en) | 2012-12-28 | 2012-12-28 | Water-based ultraviolet curing resin, coating based on water-based ultraviolet curing resin and medical catheter |
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| CN110237309A (en) * | 2019-06-24 | 2019-09-17 | 山东吉威医疗制品有限公司 | A kind of hydrophilic coating solution and preparation and application for foley's tube |
| CN110845666B (en) * | 2019-11-07 | 2022-03-04 | 北京美中双和医疗器械股份有限公司 | Functionalized hydrophilic polymer, hydrophilic coating solution and medical catheter comprising the same |
| CN110975017A (en) * | 2019-11-14 | 2020-04-10 | 北京迪玛克医药科技有限公司 | Photocurable hydrophilic coating material for interventional instrument, and preparation method and application thereof |
| CN111303618A (en) * | 2019-12-20 | 2020-06-19 | 山东一诺威聚氨酯股份有限公司 | Organic silicon modified TPU medical catheter and preparation method thereof |
| CN112480350B (en) * | 2020-11-06 | 2022-04-05 | 中国科学院化学研究所 | Hydrophilic polyurethane, preparation method thereof, biological printing composite material and application |
| CN113405870A (en) * | 2021-06-16 | 2021-09-17 | 上海蓝盎医学科技发展有限公司 | New method for sealing sheet |
| CN116162405B (en) * | 2023-04-21 | 2023-07-21 | 上海发微医用材料有限公司 | Single layer hydrophilic coating and formulation system and implantable medical device thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1710002A (en) * | 2005-06-16 | 2005-12-21 | 武汉科利尔化工有限公司 | Water-based polyurethane resin and its electrophoretic paint composition and preparing method |
| CN101544741A (en) * | 2009-04-30 | 2009-09-30 | 上海大学 | Method for preparing dianion type water-based light-cured polyurethane resin through chain extending method |
| CN102250309A (en) * | 2011-06-16 | 2011-11-23 | 新丰见微化工实业有限公司 | Flame-retarding ultraviolet curing aqueous polyurethane coating and preparation method thereof |
-
2012
- 2012-12-28 CN CN201210582216.4A patent/CN102993407B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1710002A (en) * | 2005-06-16 | 2005-12-21 | 武汉科利尔化工有限公司 | Water-based polyurethane resin and its electrophoretic paint composition and preparing method |
| CN101544741A (en) * | 2009-04-30 | 2009-09-30 | 上海大学 | Method for preparing dianion type water-based light-cured polyurethane resin through chain extending method |
| CN102250309A (en) * | 2011-06-16 | 2011-11-23 | 新丰见微化工实业有限公司 | Flame-retarding ultraviolet curing aqueous polyurethane coating and preparation method thereof |
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