CN102993407A - 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 that obtains of this resin, so that the medical catheter for preparing.
Background technology
The 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 in human body, the surface that all needs to have oilness is to avoid damaging in-vivo tissue.
With regard to general material, namely use Precision Method processing to obtain smooth even curface, 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 cause the interruption of interventional programs because of moving the very large resistance of experience in human body natural cavity organization, be difficult to satisfy service requirements.
Polymer materials is easy to carry out modification or grafting is processed, and can improve its surface property by surface treatment, improves oilness and the biocompatibility of material, and therefore, polymer materials more and more is applied to making the 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 making employed medicine equipment in the intervention diagnosis and therapy.Present stage, for the manufacture of the used urethane of medicine equipment be a kind of polyether-type polyurethane(s), recently developed again the urethane that is separated (SPU).
Although the medicine equipment that uses the polyurethane material manufacturing to obtain has preferably characteristic, its surface lubrication is Shortcomings still, and the adsorptivity of thrombocyte and protein is still existed, and remains further to be improved.By polyurethane material being carried out surface modification treatment to improve its performance, it is more common a kind of scheme.
It is coating modified to adopt urethane (PUR)/polyvinylpyrrolidone (PVP) interpenetrating network system that the PUR material surface is carried out such as people such as Wu Zengyong, has studied the PVP of different content to the impact of the performances such as coatingsurface pattern, water-absorbent, oilness, stability.The result shows: the lubricity of material surface obviously improves after the modification, and when the PVP massfraction was 2.5%, frictional coefficient 0.45 before by modification dropped to 0.074; The coating stability is better.The human UV-light such as Luo Xianglin 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 surface-treated simultaneously, the new problem of also bringing, not high such as the sticking power of coating, be easy to come off, this has also limited its application and popularization.In China, high-end interventional medical apparatus is commonly Overseas Company, and such as monopolizations such as Japanese Terumo Corp, price is high.Simultaneously, existing method of modifying is comparatively complicated, and production cost is higher.
Medical apparatus surface is material modified to be necessary to develop a kind of novel being used for.
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 kind of water base UV cured resin, its preparation method is as follows:
1) polycaprolactone glycol is dried to water content and is not higher than 0.05%, temperature adjustment to 30～70 ℃;
2) protection of protection gas is lower, adds 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, 60～70 ℃ of lower acrylate monomers that drip hydroxyls, react complete after, obtain the urethane acrylate multipolymer;
5) add the neutralizing agent remaining carboxyl that neutralizes fully at the urethane acrylate multipolymer, add water-dispersion and remove residual organic solvent, obtain water base UV cured resin;
Wherein,
The NCO of diphenylmethanediisocyanate base: 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, after the acid of adding dihydroxymethyl, 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.
A kind of UV solidifies 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 an amount of light trigger, defoamer, flow agent, and use aqueous solvent to regulate its viscosity;
Wherein, water base UV cured resin is as described in the above-mentioned any one.
As a further improvement on the present invention, vinyl silanes is selected from vinyl trimethylsilane and vinyltrimethoxy silane.
A kind of medical catheter, catheter surface are solidified with above-mentioned UV and solidify 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 the polyurethane high molecule material, simultaneously, has well biocompatibility.
Hydrophilic lubrication coating of the present invention, after UV-irradiation, free radicals copolymerization reaction will occur in urethane acrylate photolytic activity oligopolymer, NVP, vinyl organosilicon, and with graft polymerization occurs through the conduit of UV-irradiation, seal wire surface, 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.In case be in aqueous environment, behind contact body fluid, the coatingsurface formation hydration layer that absorbs water rapidly significantly reduce the friction resistance of apparatus in moving process, and the wetting ability slip coating does not come off when intubate.
Medical catheter of the present invention, be easy to preparation, its surface can form the hydration layer with oilness after meeting water, its frictional coefficient is lower than 0.1, have 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 kind of water base UV cured resin, its preparation method is as follows:
1) polycaprolactone glycol is dried to water content and is not higher than 0.05%, temperature adjustment to 30～70 ℃;
2) protection of protection gas is lower, adds 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, 60～70 ℃ of lower acrylate monomers that drip hydroxyls, react complete after, obtain the urethane acrylate multipolymer;
5) add the neutralizing agent remaining carboxyl that neutralizes fully at the urethane acrylate multipolymer, add water-dispersion and remove residual organic solvent, obtain water base UV cured resin;
Wherein,
The NCO of diphenylmethanediisocyanate base: 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 the aforesaid method, OH base among the polycaprolactone glycol PCL and the NCO radical reaction of diphenylmethanediisocyanate MDI generate base polyurethane prepolymer for use as, add afterwards dihydroxymethyl acid and carry out modification, add afterwards the further modification of acrylate monomer of hydroxyl, obtain the UV cured resin.Organic solvent that be used for to regulate base polyurethane prepolymer for use as A viscosity can conventional organic solvent, it is preferred that those are harmless to human body basic, with water compatible again not can with the organic solvent of isocyanate reaction, such 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, after the acid of adding dihydroxymethyl, 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.
A kind of UV solidifies 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 an amount of light trigger, defoamer, flow agent, and use aqueous solvent to regulate its viscosity;
Wherein, water base UV cured resin is as described in the above-mentioned any one.
The aqueous solvent that is used for adjusting coating viscosity can be the mixing solutions of lower alcohol and water, in the 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 kind of medical catheter, catheter surface are solidified with above-mentioned UV and solidify hydrophilic lubrication coating.
The application of coating can be adopted following method:
1) scrub is used on the polyurethane base material surface, shone certain hour under the ultraviolet light;
2) base material is immersed water-based ultraviolet (UV) curable coating, stop certain hour, make its surface coating paint;
3) take out base material, place air to its surface drying;
4) use UV-irradiation coating, coating is solidified fully.
Concrete application is as follows:
The wipes of alcohol wash clean is used on the polyurethane base material surface, put into 2 mw/ cm
2Ultraviolet light under irradiation 2 minutes, then immerse water-based ultraviolet (UV) curable coating with 2cm/ speed second, stopped 5 seconds, take out with 0.5cm/ speed second 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 with carboxyl neutralization residual in the UV cured resin, is for the aqueous dispersions integral body that makes resin is neutral or alkalescence on the weak side, avoids that NVP is hydrolyzed to acetaldehyde and pyrrolidone in the coating process.For achieving the above object, by regulating the amount of neutralizing agent, the pH regulator to 7.0 of UV resin aqueous dispersions～7.5 are got final product.The example of the neutralizing agent that this area is common has triethylamine, also can use other neutralizing agent neutralization.
Produce too much foam when mixing in order to reduce, affect the performance of coating, in the mixing process of coating, can add an amount of 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 place after conventional the mixing and carry out defoaming treatment under the condition of negative pressure, can further reduce the consumption of defoamer, even need not to add defoamer.Because the singularity of application of paints occasion, the preferred harmless defoamer of defoamer, such as organic silicon defoaming 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 specify the present invention.
In following examples:
Employed polycaprolactone glycol is all predrying to be less than 0.05% to the biodiversity relative content, and its manufacturer is Japanese Daisel chemical industry Co., Ltd;
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 after solidifying;
Press the adhere firmly degree of GB/T 13217.7-2009 mensuration coating.
Embodiment 1
1, synthetic water base UV cured resin
1) taking by weighing 100 grams average molecular weights is 500 polycaprolactone glycol (altogether about 0.2mol) (trade mark: PCLL205AL); be warming up to 30 ℃; add altogether about 0.40mol of 100.4 gram diphenylmethanediisocyanate MDI(at nitrogen atmosphere protection and under stirring) reaction 2.5h
2) be warming up to 70～80 ℃, add again 16.0 gram dimethylolpropionic acid DM
BA(is about 0.11mol altogether), reaction 2h obtains base polyurethane prepolymer for use as A;
3) add 23 gram acetone viscosity reductions in base polyurethane prepolymer for use as A, then drip 21.6 gram acrylate hydroxyl ethyl ester monomers, temperature of reaction is controlled at 65 ℃, drips off at 55 minutes;
4) cool the temperature to room temperature, obtain the urethane acrylate multipolymer;
5) under stirring at room, add 11.1 gram triethylamines in the above-mentioned multipolymer and 525 gram water 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, namely gets 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 that band stirs, take by weighing the above-mentioned water base UV cured resin of 35 grams, 25 gram NVPs, start stirring, under agitation, add 0.1 gram defoamer BYK020,0.2 gram flow agent BYK333,0.5 gram vinyl trimethylsilane, 18 gram ethanol and 19.2 gram deionized waters, add at last 2 gram light trigger alpha-hydroxyacetophenones, after stirring, make water-based ultraviolet (UV) curable wetting ability slip coating.
Using under 25 ℃ and being coated with 4 glasss of viscosity of measuring these coating is 18 seconds.
3, the application of coating and curing
Choose the TPU58680 polyurethane base material that U.S. Noveon Asia-Pacific company limited produces, then the wipes of alcohol wash clean is used on its surface, put into 2 mw/ cm
2Ultraviolet light under irradiation 2 minutes, then immerse water-based ultraviolet (UV) curable coating with 2cm/ speed second, stopped 5 seconds, again 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, obtain coating at the TPU surface cure at last.
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) taking by weighing 100 grams average molecular weights is 850 polycaprolactone glycol (altogether about 0.12mol) (trade mark: PCL308), be warming up to 45 ℃, add altogether about 0.39mol of 98.2 gram diphenylmethanediisocyanate MDI(at nitrogen atmosphere protection and under stirring) reaction 2.5 h;
2) be warming up to 70～80 ℃, add again altogether about 0.10mol of 14.9 gram dimethylolpropionic acid DMBA(), reaction 2h obtains base polyurethane prepolymer for use as A;
3) add 12.5 gram acetone viscosity reductions in base polyurethane prepolymer for use as A, then drip 49.5 gram acrylate hydroxypropyl acrylate monomers, temperature of reaction is controlled at 65 ℃, drips off at 55 minutes;
4) cool the temperature to room temperature, obtain the urethane acrylate multipolymer;
5) under stirring at room, add 11.1 gram triethylamines in the above-mentioned multipolymer and 432 gram water 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, namely gets 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 that band stirs, take by weighing the above-mentioned water base UV cured resin of 38 grams, 50 gram NVPs, start stirring, under agitation, add 0.5 gram BYK020 defoamer, 0.2 gram BYK333 flow agent, 1.5 gram vinyl trimethylsilane, 15 gram Virahols and, 14.8 gram deionized waters, add at last 1.5 grams 2,2-dimethyl-2-hydroxy acetophenone after stirring, makes water-based ultraviolet (UV) curable wetting ability slip coating.
Using under 25 ℃ and being coated with 4 glasss of viscosity of measuring these coating is 19 seconds.
Choose the TPU58680 polyurethane base material that U.S. Noveon Asia-Pacific company limited produces, then the wipes of alcohol wash clean is used on its surface, put into 2 mw/ cm
2Ultraviolet light under irradiation 2 minutes, then immerse water-based ultraviolet (UV) curable coating with 2cm/ speed second, stopped 5 seconds, again 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, obtain coating at the TPU surface cure at last.
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) taking by weighing 100 grams average molecular weights is 1000 polycaprolactone glycol (altogether about 0.1mol) (trade mark: PCL210N), be warming up to 60 ℃, add altogether about 0.26mol of 64.6 gram diphenylmethanediisocyanate MDI(at nitrogen atmosphere protection and under stirring) reaction 1.5 h;
2) be warming up to 70～80 ℃, add again altogether about 0.06mol of 8.23 gram dimethylol propionic acid DMPA(), react 1.5 h, obtain base polyurethane prepolymer for use as A;
3) add 18.9 gram DMF viscosity reductions in base polyurethane prepolymer for use as A, then drip 24.7 gram methacrylic ester hydroxyl ethyl ester monomers, temperature of reaction is controlled at 65 ℃, drips off at 50 minutes;
4) cool the temperature to room temperature, obtain the urethane acrylate multipolymer;
5) under stirring at room, add 6.27 gram triethylamines in the above-mentioned multipolymer and 333 gram water 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, namely gets 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 that band stirs, take by weighing the above-mentioned water base UV cured resin of 10 grams, 20 gram NVPs, start stirring, under agitation, add 0.3 gram TEGO825 defoamer, 0.2 gram TEGO410 flow agent, 0.5 gram vinyl trimethylsilane, 12 gram ethanol and, 18.7 gram deionized waters, add at last 1.0 gram α-UVINUL MS 40-sodium sulfonates, after stirring, make water-based ultraviolet (UV) curable wetting ability slip coating.
Using under 25 ℃ and being coated with 4 glasss of viscosity of measuring these coating is 16 seconds.
Choose the TPU58680 polyurethane base material that U.S. Noveon Asia-Pacific company limited produces, then the wipes of alcohol wash clean is used on its surface, put into 2 mw/ cm
2Ultraviolet light under irradiation 2 minutes, then immerse water-based ultraviolet (UV) curable coating with 2cm/ speed second, stopped 5 seconds, again 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, obtain coating at the TPU surface cure at last.
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) taking by weighing 100 grams average molecular weights is 2000 polycaprolactone glycol (altogether about 0.05 mol) (trade mark: PCL220N), be warming up to 70 ℃, add altogether about 0.17 mol of 42.2 gram diphenylmethanediisocyanate MDI(at nitrogen atmosphere protection and under stirring) reaction 2 h;
2) be warming up to 70～80 ℃, add 5.86 gram dimethylol propionic acid DMPA again, reaction 1.5h obtains base polyurethane prepolymer for use as A;
3) add 16 gram ethyl acetate viscosity reductions in base polyurethane prepolymer for use as A, then drip 19.5 gram methacrylic ester hydroxypropyl acrylate monomers, temperature of reaction is controlled at 70 ℃, drips off at 60 minutes;
4) cool the temperature to room temperature, obtain the urethane acrylate multipolymer;
5) under stirring at room, add 4.45 gram triethylamines in the above-mentioned multipolymer and 555 gram water 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, namely gets 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 that band stirs, take by weighing the above-mentioned water base UV cured resin of 50 grams, 40 gram NVPs, start stirring, under agitation, add 0.08 gram TEGO825 defoamer, 0.20 gram TEGO410 flow agent, 3.0 gram vinyltrimethoxy silanes, 25.0 gram ethanol and, 15.9 gram deionized waters, add at last 2.5 gram α-UVINUL MS 40-sodium sulfonates, after stirring, make water-based ultraviolet (UV) curable wetting ability slip coating.
Using under 25 ℃ and being coated with 4 glasss of viscosity of measuring these coating is 19 seconds.
Choose the TPU58680 polyurethane base material that U.S. Noveon Asia-Pacific company limited produces, then the wipes of alcohol wash clean is used on its surface, put into 2 mw/ cm
2Ultraviolet light under irradiation 2 minutes, then immerse water-based ultraviolet (UV) curable coating with 2cm/ speed second, stopped 5 seconds, again 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, obtain coating at the TPU surface cure at last.
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 (10)
1. water base UV cured resin, its preparation method is as follows:
1) polycaprolactone glycol is dried to water content and is not higher than 0.05%, temperature adjustment to 30～70 ℃;
2) protection of protection gas is lower, adds 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, 60～70 ℃ of lower acrylate monomers that drip hydroxyls, react complete after, obtain the urethane acrylate multipolymer;
5) add the neutralizing agent remaining carboxyl that neutralizes fully at the urethane acrylate multipolymer, add water-dispersion and remove residual organic solvent, obtain water base UV cured resin;
Wherein,
The NCO of diphenylmethanediisocyanate base: 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.
2. water base UV cured resin according to claim 1, it 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, it is characterized in that: dihydroxymethyl acid is selected from dimethylol propionic acid and dimethylolpropionic acid.
4. water base UV cured resin according to claim 1 and 2, it is characterized in that: the acrylate monomer of hydroxyl is selected from Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate and Rocryl 410.
5. water base UV cured resin according to claim 1 and 2, it is characterized in that: the time of polycaprolactone glycol and diphenylmethanediisocyanate polyreaction is 1.5～2.5h.
6. water base UV cured resin according to claim 1 and 2 is characterized in that: after adding dihydroxymethyl acid, continue reaction 1.5h～2h.
7. water base UV cured resin according to claim 1 and 2, it is characterized in that: total time for adding of the acrylate monomer of hydroxyl is controlled at 50～60min.
8. a UV solidifies 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 an amount of light trigger, defoamer, flow agent, and use aqueous solvent to regulate its viscosity;
Wherein, water base UV cured resin is as described in claim 1～7 any one.
9. UV according to claim 8 solidifies hydrophilic lubrication coating, and it is characterized in that: vinyl silanes is selected from vinyl trimethylsilane and vinyltrimethoxy silane.
10. medical catheter is characterized in that: described catheter surface is solidified with above-mentioned UV and solidifies hydrophilic lubrication coating.
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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 |
| CN110845666A (en) * | 2019-11-07 | 2020-02-28 | 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 |
| CN112480350A (en) * | 2020-11-06 | 2021-03-12 | 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 |
| CN116162405A (en) * | 2023-04-21 | 2023-05-26 | 上海发微医用材料有限公司 | Single layer hydrophilic coating and formulation system and implantable medical device thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110845666A (en) * | 2019-11-07 | 2020-02-28 | 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 |
| 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 |
| CN112480350A (en) * | 2020-11-06 | 2021-03-12 | 中国科学院化学研究所 | Hydrophilic polyurethane, preparation method thereof, biological printing composite material and application |
| 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 |
| CN116162405A (en) * | 2023-04-21 | 2023-05-26 | 上海发微医用材料有限公司 | Single layer hydrophilic coating and formulation system and implantable medical device thereof |
| 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 |
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