CN105985721A - Paint for forming hydrophilic coating on surface of catheter, and preparation and application methods thereof - Google Patents
Paint for forming hydrophilic coating on surface of catheter, and preparation and application methods thereof Download PDFInfo
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- CN105985721A CN105985721A CN201510073639.7A CN201510073639A CN105985721A CN 105985721 A CN105985721 A CN 105985721A CN 201510073639 A CN201510073639 A CN 201510073639A CN 105985721 A CN105985721 A CN 105985721A
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Abstract
The invention relates to a paint for forming a hydrophilic coating on the surface of a catheter, and preparation and application methods thereof. The paint comprises a prime paint and a top paint; the prime paint comprises aqueous polyurethane, a multi-functionality aziridine derivative and deionized water; and the top paint comprises side carboxyl polyurethane, polymethyl vinyl ether-maleic anhydride and an organic solvent. During curing, all the components form a crosslinking structure; the bottom and the top of the coating are tightly bonded through a covalent bond, and the coating is firmly adhered on the surface of the catheter; and the coating has excellent hydrophilic lubricity and wear resistance, and is applicable to hydrophilic lubrication treatment of apparatuses like an intervention catheter for TCM treatment in the technical field of endovascular intervention diagnosis and treatment technology.
Description
Technical field
The present invention relates to medical instruments field, be specifically related to a kind of coating forming catheter surface hydrophilic coating and preparation and
Using method.
Background technology
Endovascular Interventions technology is widely used in clinical vascular radiography, angioplasty, Intravascular Thrombus or foreign body
The aspects such as removing, compared with tradition medical skill, the most easy to operate, and owing to the wound of interventional therapy is low, it is possible to
Alleviating the misery of patient, Operative risk is less, and medical expense is relatively low, and therefore this technology obtains at medical domain
Promote widely and use.Endovascular Interventions technology be by mean of interposing catheter by vessel lumen arrive internal relatively
Remote diseased region, such as vascular sites such as coronary artery, reinjects diagnosis and treatment agent or inserts apparatus, with reach to internal farther out
Position realizes the purpose of diagnosis and minimally-invasive treatment.Research of Intravascular Catheterization is one of main apparatus of endovascular temporary embolization,
Its kind can have radiography interposing catheter, medicine to carry interposing catheter, angioplasty interposing catheter etc., and these interventions are led
Pipe typically has excellent operability and safety, needs excellent blood compatibility, kink resistance and mechanical performance,
Ooze out without nuisance, good machinability, and with X-ray opacifying agent, there is the good compatibility.
Lubricity is one of highly important performance of Research of Intravascular Catheterization.When conduit is entering, exiting blood vessel and at blood
In pipe during motion, high-lubricity can suppress gluing at material surface such as the macromole in blood such as plasma protein, platelet etc.
Attached, reduce blood vessel wall and the damage of hemocyte, alleviate the disturbance to blood laminar flow, the generation of Coagulation test can be avoided.
Also can alleviate the misery that patient is caused.Therefore, it is the most necessary for interposing catheter carries out surface lubrication processing.Coating
Hydrophilic lubrication coating is to improve the effective means of interposing catheter lubricity.Utilize containing a large amount of pyrrolidone groups, oxidation second
The high-hydrophilic that thiazolinyl group, carboxyl, the polymer of amide groups show in blood, the film forming matter as coating is permissible
Reach the purpose of high-efficiency lubricating, this base polymer include polyvinyl pyrrolidone (PVP), polyethylene glycol oxide (PEO),
Acrylamido copolymer, acrylic copolymer and maleic anhydride analog copolymer etc..
For the coating on hydrophilic lubrication interposing catheter, owing to conduit to carry out moving and stop a timing in human body
Between, therefore except meeting high hydrophilic lubrication performance, also need to focus on the firm and stable of greasy property, the hydrophilic segment of coating
Will not fall off after standing repeatedly to rub with coating integral part, and maintain good combination property.It is particularly applied to
On the intervention apparatus such as seal wire, foley's tube, guiding catheter.Utilize covalent bond to connect or the means such as crosslinking can be to hydrophiling
Compound plays certain fixation, and this type of technology is the most gradually widely used.At the coating body that chemical reaction solidification occurs
In system, according to whether participating in reaction, hydrophilic compounds can be divided into again response type and non-reactive, such as PVP, PEO
For non-reactive, acrylic acid, the copolymer etc. of maleic acid anhydride are response type.
Hydrophilic coating system in early days does not the most use chemical reaction when solidification, such as United States Patent (USP) US 4589873,
US 4835003, US 4875287, US 5331027, US 5509899, US 5620738 and US 6042876 are the most public
Having opened the hydrophilic lubrication coating containing PVP, the feature of this type coating is, top layer is coated with PVP, but PVP place is coated with
Layer or its base coat the most do not introduce cross-linked structure, and PVP easily comes off after imbibition, can make whole coating system
Lose the effect of hydrophilic lubrication.
United States Patent (USP) US 8287890B2, US 6299980B1, US 5776611, US 5179174, US 5160790
All disclose with isocyanate crosslinking as base coat with US 4666437, top layer coats the hydrophilic height such as PVP or PEO
The coating system of molecule, the feature of this type coating is, in top coat in addition to containing hydrophilic high mol, being also added into can
To crosslink polyhydric alcohol or the polyamine of reaction with bottom isocyanate crosslinking, thereby serve to certain fixing work
With.But due to PVP or PEO the cross-linking reaction that is not involved in system, through friction after imbibition, the most very
Easily come off from coated substrate.
United States Patent (USP) US 8039524 B2, US 7696259 B2, US7534495 B2, US 7052131 B2, US
8378011 B2, US 8512795 B2 and US 8513320 B2 all disclose with the hydrophilic height such as double bond compound and PVP
The UV curing system coating of molecular composition.The feature of this type coating is, double bond compound is acrylic monomer,
It is coated after mixing with hydrophilic high mol, light trigger etc. under the dissolution of solvent, is obtained by ultraviolet light polymerization double
The cross-linked structure of key.But what the hydrophilic high mols such as the PVP of employing non-reactive came off after still there is water suction friction asks
Thin film fragility after topic, and double bond compound crosslinking is relatively big, and mechanical property is poor, the most poor to the tack of base material.
Additionally, compared with conventional curing mode, coating processes and the coating equipment of apparatus are required higher by ultraviolet light polymerization.
For response type hydrophilic compounds system, mainly contain N-[2-(2-methyl-4-oxopentyl)-DMAA copolymer,
Acrylic acid-acrylamide copolymer, glycidyl methacrylate-DMAA copolymer, methyl ethylene
Ether-copolymer-maleic anhydride etc..
United States Patent (USP) US 6540698 B1 reports with homemade N-[2-(2-methyl-4-oxopentyl)-DMAA copolymer
As hydrophilic high mol, being dissolved in oxolane obtaining solution, conduit immerses in solution, immerses carbon after drying again
In the aqueous solution of acid dihydrazide, pH value is adjusted to 3, utilizes the reaction of carbonyl and hydrazides to cross-link.But in this individual system,
Only using N-[2-(2-methyl-4-oxopentyl)-DMAA copolymer as film forming matter, it is poor to the tack of base material,
Easily come off under rubbing action.
United States Patent (USP) US 5804318 reports homemade containing primary amine or the acrylamide copolymer of tertiary amine group, with containing ring
Epoxide silicone coupling agents or aldehyde compound, as cross-linking agent, can first coat containing epoxy radicals silicone coupling agents, repaste
Copolymer, or first it is coated with copolymer, then immerse in aldehyde compound solution.But this coating is only made with the copolymer of crosslinking
For film forming matter, its adhesive force is the most relatively low.
Method disclosed in United States Patent (USP) US 6558798 B2 be aqueous polyurethane is mixed with aziridine crosslinker CX100 after
Be coated on equipment surfaces, to be coated half-dried after, coat acrylic acid-acrylamide copolymer, and then form crosslinking with bottom
Structure.Acrylic acid-acrylamide copolymer generally need to make acquisition by oneself, is with acrylic acid as raw material, and acrylic acid is for having corruption
Erosion property and the compound of toxicity, even if a small amount of residual also can produce harm to human body, the monomer simultaneously remained is containing irritant
Abnormal smells from the patient.Disclosed in United States Patent (USP) US 6468649 B1, technology is similar with US 6558798 B2, the primary raw material used
Also it is aqueous polyurethane, aziridine crosslinker CX100 and acrylic acid-acrylamide copolymer, there is also similar
Defect.
The method of United States Patent (USP) US 8455094 B2 and Chinese patent CN 102264403 A report is all to use plasma
Body radiation and the method for high-temperature process, be first grafted to mercaptan compound on conduit, be coated with homemade metering system
Acid glycidyl ester-DMAA copolymer, makes copolymer also graft on conduit after hot setting.This is coated with
The coating processes condition of layer is the harshest, makes the use of a lot of conduit base material be restricted owing to treatment temperature is higher, with
Time need expensive equipment.
Methyl vinyl ether-maleic acid copolymer has been widely used in fields such as medicine and food, and it is to human non-toxic,
There is after esterification hydrophilic carboxyl, be similarly applied to hydrophilic coating.
United States Patent (USP) US 5891109 reports and vinyl ether-maleic acid copolymer, polyurethane, butanone is formed
Coating, through hot setting after coating conduit, then immerses open loop in ethanol or methylamine water solution, obtains the conduit of hydrophilic lubrication.
But the anhydride group on this system medium vinyl ether-copolymer-maleic anhydride can only go out with minimal amount of polyurethane pyrolytic
The isocyanate groups come reacts, and crosslinking degree is the highest, and therefore coating fastness is the most poor, and hot setting
Condition makes it unsuitable for for most polymeric catheter and apparatus.
United States Patent (USP) US 5229211 discloses a kind of interventional medical device, equipment surfaces have maleic anhydride analog copolymer with
The coating that isocyanate prepolymer obtains after covalent bond connects, the ground of coating is polymer, selected from polrvinyl chloride, gathers
Urethane, polyamide or polyester, it takes a single example in an embodiment, will polrvinyl chloride, the 4 of micromolecular compound, 4'-bis-
Methylenebis phenyl isocyanate, oxolane composition solution, coats conduit, is coated with methyl vinyl ether-horse after drying
Carry out acid anhydride copolymer, immerse sodium salt solution and hot wash after solidification, obtain hydrophilic lubrication conduit.But the end in this system
Material is not connected by chemical reaction with other components, thus coating fastness is the most not enough.Additionally, isocyanation esterification
Compound has toxicity, health can be caused potential safety hazard.
It will be seen that relative to the hydrophilic high mol of non-reactive, the hydrophilic high mol of response type has more preferable coating jail
Solidity, but other the most matched components are the most closely connected with each other, and conduit is lacked enough
Adhesive force, coating yet suffers from the problem that wearability is not enough, it is therefore desirable to build new coating architecture to realize getting involved
Conduit not only hydrophilic lubrication but also wear-resisting purpose, it is still necessary to provide new technology to obtain the catheter coatings of higher performance.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of coating forming catheter surface hydrophilic coating and preparation thereof and makes
Use method.Purpose is to confer to the excellent Hydrophilic lubrication of interposing catheter and wearability.
The present invention, by building two layer coating system, utilizing chemical bond to connect formation many components cross-linked structure, had both served and had made
Coating outer surface has the effect of hydrophilic lubrication, in turn ensure that bottom coating with the firm attachment of conduit and bottom and top
Between combine closely, make crocking resistance excellent.
Further summary is exactly, owing to high hydrophilic lubrication sexual needs coating outer surface to possess substantial amounts of hydrophilic group, and lance
Shield, if hydrophilic polymer too high levels in system, then the fastness of this film forming matter is inevitable poor, in the present invention
The method solved builds duplex coating exactly, and the crosslinking of painting interlayer, i.e. top layer have the hydrophilic polymer of high-load i.e.
Polymethyl vinyl ether-maleic anhydride and a small amount of containing side carboxyl polyurethane, bottom comprises has preferable adhesive force with conduit
Aqueous polyurethane and the intermediate medium i.e. polyfunctionality aziridine derivative of upper and lower two layers of coatings can be connected.In order to make
Polymethyl vinyl ether-maleic anhydride can react with aziridine group, uses poly glycol monomethyl ether and part
Maleic groups generation esterification, is grafted on the molecular skeleton of polymethyl vinyl ether-maleic anhydride, obtains simultaneously
Obtain the carboxyl that can react with aziridine group, and the Oxyerhylene on poly glycol monomethyl ether may also operate as parent
The effect of water.So, the polyurethane in coating and polymethyl vinyl ether-maleic anhydride are spread out by polyfunctionality aziridine
Biological crosslinked action forms close entirety, and the fastness of hydrophilic coating is greatly promoted.
Above-mentioned purpose can be realized by technical scheme in detailed below:
A kind of coating forming catheter surface hydrophilic coating, it is characterised in that coating comprises subbing and top coat paint,
Described subbing is made up of aqueous polyurethane, polyfunctionality aziridine derivative and deionized water, wherein polyfunctionality
The quality of aziridine derivative is the 1%~10% of aqueous polyurethane quality, and the quality of deionized water is subbing gross mass
80%~99%, described top coat paint is by containing side carboxyl polyurethane, polymethyl vinyl ether-maleic anhydride, poly-second two
Alcohol monomethyl ether and organic solvent composition, wherein containing the mass ratio of side carboxyl polyurethane with polymethyl vinyl ether-maleic anhydride
For 1:(0.1~10), the quality of poly glycol monomethyl ether is the 1%~20% of polymethyl vinyl ether-maleic anhydride quality, organic
The quality of solvent is the 80%~99% of top coat paint gross mass.
The described coating forming catheter surface hydrophilic coating, it is characterised in that described polyfunctionality aziridine derivative
For trimethylolpropane-three [3-(2-methylaziridine base)] propionic ester, trimethylolpropane-three (3-'-aziridino) propionic ester,
One or more in tetramethylolmethane-three (3-'-aziridino) propionic ester.
The described coating forming catheter surface hydrophilic coating, it is characterised in that the described molecule containing side carboxyl polyurethane
Chain structure is through additive reaction by polyethers or polyester diol, diisocyanate, 2,2-dihydromethyl propionic acid and 1,4-butanediol
Connected, described polyethers or polyester diol be polyoxypropyleneglycol, polytetrahydrofuran diol, PCDL,
One in polycaprolactone glycol, number-average molecular weight is 1000~4000, and described diisocyanate is 2,4-toluene diisocyanate
In acid esters, hexa-methylene 1,6-diisocyanate, 4,4'-methyl diphenylene diisocyanate, isophorone diisocyanate
One.
The described coating forming catheter surface hydrophilic coating, it is characterised in that described organic solvent is N, N-dimethyl
Methanamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, N, N-dimethyl sulfoxide, ethyl acetate, butyl acetate,
One or more in dichloromethane, chloroform, acetone, butanone, oxolane.
The preparation method of a kind of described coating forming catheter surface hydrophilic coating, it is characterised in that comprise the steps:
(1) preparation containing side carboxyl polyurethane: use solvent method synthesis polyurethane Han side carboxyl, by polyethers or polyester two
Unit's alcohol and diisocyanate add in reactor, are warming up to 80 DEG C, and stirring reaction obtained performed polymer after 1 hour, added 2,2-
Dihydromethyl propionic acid and BDO, after reacting 2 hours, add DMF, after continuing reaction 1 hour,
Add dibutyl tin laurate, then react 8 hours, be down to room temperature, solution in reactor is poured into equipped with deionized water
Container in, have white depositions to separate out, collect precipitate and be also washed with deionized 3 times, be positioned over vacuum drying and dry
In case, it is vacuum dried 48 hours at 90 DEG C, obtains transparent cake product, obtain after its pelletize containing side carboxyl polyurethane
Masterbatch, wherein, the molal quantity of described diisocyanate and polyethers or polyester diol, 2,2-dihydromethyl propionic acid and Isosorbide-5-Nitrae-
The ratio of the total mole number of butanediol is (1.05~1.2): 1,2,2-dihydromethyl propionic acid with the ratio of the molal quantity of BDO is
The quality of 1:1, polyethers or polyester diol and diisocyanate, 2,2-dihydromethyl propionic acid and the gross mass of BDO
Ratio be (1.5~1): 1, the quality of DMF is 4:1 with the ratio of the gross mass of other all raw materials, two Laurels
The quality of acid dibutyl tin is polyethers or the 1% of polyester diol quality, the quality of deionized water used and N, N-during precipitation
The mass ratio of dimethylformamide is 2:1, every time the quality of deionized water used and DMF during washing
Mass ratio be 2:1;
(2) preparation of subbing: aqueous polyurethane, polyfunctionality aziridine derivative, deionized water are added extremely
In container, being stirred at room temperature 30 minutes, obtain subbing, wherein the quality of polyfunctionality aziridine derivative is water
The 1%~10% of property polyurethane quality, the quality of deionized water is the 80%~99% of subbing gross mass;
(3) preparation of top coat paint: side carboxyl polyurethane, polymethyl vinyl ether-maleic anhydride, Polyethylene Glycol will be contained
Monomethyl ether, organic solvent add to container, are stirred at room temperature 30 minutes, obtain top coat paint, wherein containing side carboxyl
Polyurethane is 1:(0.1~10 with the mass ratio of polymethyl vinyl ether-maleic anhydride), the quality of poly glycol monomethyl ether is poly-
The 1%~20% of methyl vinyl ether-maleic acid quality, the quality of organic solvent be top coat paint gross mass 80%~
99%.
The preparation method of the described coating forming catheter surface hydrophilic coating, it is characterised in that described in step (1)
Polyethers or polyester diol be polyoxypropyleneglycol, polytetrahydrofuran diol, PCDL, polycaprolactone two
One in alcohol, number-average molecular weight is 1000~4000, and described diisocyanate is 2,4 toluene diisocyanate, six Asias
One in methyl 1,6-diisocyanate, 4,4'-methyl diphenylene diisocyanate, isophorone diisocyanate.
The preparation method of the described coating forming catheter surface hydrophilic coating, it is characterised in that described in step (2)
Polyfunctionality aziridine derivative be trimethylolpropane-three [3-(2-methylaziridine base)] propionic ester, trihydroxy methyl third
One or more in alkane-three (3-'-aziridino) propionic ester, tetramethylolmethane-three (3-'-aziridino) propionic ester.
The preparation method of the described coating forming catheter surface hydrophilic coating, it is characterised in that described in step (3)
Organic solvent be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, N, N-dimethyl
One in sulfoxide, ethyl acetate, butyl acetate, dichloromethane, chloroform, acetone, butanone, oxolane or
Several.
The using method of a kind of described coating forming catheter surface hydrophilic coating, it is characterised in that comprise the steps:
(1) coating coating processing: by subbing by dip-coating, spray or brush in the way of coat the surface to conduit,
Solidify at 60 DEG C 1 hour, afterwards by top coat paint coating to the conduit having been coated with subbing, at 80 DEG C, solidify 1
Hour, obtain outer surface and be coated with the conduit of cross-linked structure coating;
(2) coating hydrophilic processes: is immersed to strong aqua ammonia by the conduit processed in step (1), at room temperature soaks
Steep 1 hour, be dried 2 hours at 60 DEG C after taking-up, surface must be arrived there is the interposing catheter of hydrophilic cross-linking structure coating.
The invention has the beneficial effects as follows:
(1) compared with prior art, the present invention efficiently solves the problem that hydrophilic coating fastness is not enough, by building
Two layer coating system and chemical bond cross-linked structure, make coating outer surface both hydrophilic lubrications, in turn ensure that the jail of bottom and conduit
Gu combining closely between attachment and bottom and top so that it is there is the wearability of excellence.The coating of the present invention is used for being situated between
After entering conduit, conduit friction can be made to reduce by more than 90%.After rubbing action repeatedly, hydrophilic coating retains complete,
Conduit friction increasing degree is less than 2%.
(2) present invention is controlled containing the raw material type in side carboxyl polyurethane synthetic reaction, consumption, reaction temperature by strict
The conditions such as degree and time, reach molecular structure, NCO and hydroxyl mol ratio, soft or hard section ratio, carboxyl-content
The purpose defined, obtains that surface is the most tacky, mechanical strength is high, product yield is high containing side carboxyl polyurethane, thus
Obtain and meet the material needed for cross-linking reaction of the present invention, compensate for other macromolecular material performances and the deficiency of function.
(3) subbing of the present invention is water solution system, it is to avoid the organic solvent corrosion to interposing catheter, and relatively
For environmental protection.Additionally, the paint solidification temperature of the present invention is relatively low, conduit will not be caused damage.Therefore the scope of application is wider.
It can be that conduit provides firm hydrophilic lubrication performance, is particularly suited for Endovascular Interventions technical field, can be used for
Medical apparatus and instruments includes that seal wire, foley's tube, guiding catheter, thrombus suction catheter, peripheral central venous catheter, radiography are led
Pipe, expansion are managed and tear sheath etc..
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
Preparation containing side carboxyl polyurethane (CPU): use solvent method synthesis polyurethane Han side carboxyl, by polyethers or polyester
Dihydroxylic alcohols and diisocyanate add in reactor, are warming up to 80 DEG C, and stirring reaction obtained performed polymer after 1 hour, added
2,2-dihydromethyl propionic acids and BDO, after reacting 2 hours, add DMF, continue reaction 1 little
Shi Hou, adds dibutyl tin laurate, then reacts 8 hours, be down to room temperature, pour solution in reactor equipped with going into
In the container of ionized water, there is white depositions to separate out, collect precipitate and be washed with deionized 3 times, being positioned over vacuum
In drying oven, it is vacuum dried 48 hours at 90 DEG C, obtains transparent cake product, obtain containing side carboxyl after its pelletize
Polyurethane masterbatch.
Wherein, described polyethers or polyester diol are selected from polyoxypropyleneglycol (PPG), polytetrahydrofuran diol
(PTMG) one, in PCDL (PCDL), polycaprolactone glycol (PCL), number-average molecular weight (Mn)
1000~4000.Described diisocyanate is 2,4 toluene diisocyanate (TDI), hexa-methylene 1,6-bis-Carbimide.
Ester (HDI), 4,4'-methyl diphenylene diisocyanate (MDI), isophorone diisocyanate (IPDI).Described two
The molal quantity of isocyanates and polyethers or the ratio of the total mole number of polyester diol, 2,2-dihydromethyl propionic acid and 1,4-butanediol
Be designated as the quality of F-a, polyethers or polyester diol and diisocyanate, 2,2-dihydromethyl propionic acid and BDO total
Mass ratio is designated as F-b, and 2,2-dihydromethyl propionic acids are 1:1 with the ratio of the molal quantity of BDO, N, N-dimethyl formyl
The quality of amine is 4:1 with the ratio of the gross mass of other all raw materials, and the quality of dibutyl tin laurate is polyether Glycols matter
The 1% of amount, during precipitation, the quality of deionized water used is 2:1 with the mass ratio of DMF, washs every time
The quality of Shi Suoyong deionized water and the mass ratio of N,N-dimethylformamide are 2:1.
Respectively as shown in table 1 containing side carboxyl polyurethane product code name, raw material and proportioning.
The respectively melt polyurethane Han side carboxyl is processed into sheet material, tests its water contact angle, it appeared that its contact angle is the most relatively low,
Carboxyl is contained on illustrative material surface.
Table 1 contains raw material and the consumption of side carboxyl polyurethane
Embodiment 2
Aqueous polyurethane, trimethylolpropane-three [3-(2-methylaziridine base)] propionic ester, deionized water are added to holding
In device, it is stirred at room temperature 30 minutes, obtains subbing, wherein trimethylolpropane-three [3-(2-methylaziridine base)]
The quality of propionic ester is the 1% of aqueous polyurethane quality, and the quality of deionized water is the 80% of subbing gross mass.To contain
Side carboxyl polyurethane CPU-1, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, N, N-dimethyl formyl
Amine adds to container, is stirred at room temperature 30 minutes, obtains top coat paint, wherein CPU-1 and polymethyl vinyl ether
The mass ratio of-maleic anhydride is 1:0.1, and the quality of poly glycol monomethyl ether is polymethyl vinyl ether-maleic anhydride quality
1%, the quality of DMF is the 80% of top coat paint gross mass.Polymethyl vinyl ether-maleic anhydride is
Sigma-Aldrich, number-average molecular weight are the product of 80000, and aqueous polyurethane is Lubrizol Corp. Sancure 777
Type product, poly glycol monomethyl ether be Sigma-Aldrich, number-average molecular weight be the product of 1000.By above-mentioned
Subbing coating, to the surface of interposing catheter, solidifies at 60 DEG C 1 hour, coats top coat paint to having been coated with afterwards
On the conduit of subbing, solidify 1 hour at 80 DEG C, obtain outer surface and be coated with the conduit of cross-linked structure coating, then
It is dipped in strong aqua ammonia, at room temperature soaks 1 hour, be dried 2 hours at 60 DEG C after taking-up, surface must be arrived and have
The interposing catheter of Hydrophilic lubrication.
Interposing catheter lubricity method of testing is as follows: the conduit half length of a length of 20cm coats above-mentioned coating, and
Second half length not coating layer, tube at one end is vertically fixed in the lower clamp of stretching-machine, clamps one at catheter surface
Self-control slide block, this slide block can be screwed on conduit and give the pressure that conduit is fixing, and the internal interlayer of slide block can carry certain body
Long-pending deionized water, can implement to infiltrate continuously to conduit, have the upper clamp of mechanics sensor to press from both sides with connecting in stretching-machine
Holding slide block, slide block is pulled to conduit top from conduit bottom according to fixed speed, then the stress change of sensor embodies conduit
In the frictional force that two kinds of surfaces are subject to, the difference of friction value reflects the Hydrophilic lubrication of conduit.Record two parts table
Friction value corresponding to center, face, then can get the amplitude that water-wetted surface frictional force reduces, be designated as fp-r, fp-r
It is worth the biggest, illustrates that lubricity is the best.
Interposing catheter abrasion resistance test method is as follows: load the conduit coating above-mentioned coating to institute in lubricity method of testing
On the equipment stated, make slide block up-and-down movement 100 times, record under fixing displacement and speed by programme-control
Initial and friction value when terminating, the difference of this friction value reflects degree that coating abrasion comes off and conduit
Wearability.The amplitude that frictional force when terminating increases is designated as fp-i, fp-i value the least, illustrates that wearability is the best.
Test result shows, in the present embodiment, conduit friction reduces degree fp-r value is 91.5%, and conduit is rubbed
It is 1.8% that rear friction increases degree fp-i value.
Embodiment 3
Aqueous polyurethane, trimethylolpropane-three (3-'-aziridino) propionic ester, deionized water are added to container,
Stirring 30 minutes under room temperature, obtain subbing, wherein the quality of trimethylolpropane-three (3-'-aziridino) propionic ester is
The 2% of aqueous polyurethane quality, the quality of deionized water is the 83% of subbing gross mass.Side carboxyl polyurethane will be contained
CPU-2, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, N,N-dimethylacetamide add to container,
It is stirred at room temperature 30 minutes, obtains top coat paint, wherein CPU-2 and the quality of polymethyl vinyl ether-maleic anhydride
Ratio is 1:0.5, and the quality of poly glycol monomethyl ether is the 3% of polymethyl vinyl ether-maleic anhydride quality, N, N-dimethyl
The quality of acetamide is the 83% of top coat paint gross mass.Polymethyl vinyl ether-maleic anhydride is that Sigma-Aldrich is public
Department, number-average molecular weight are the product of 80000, and aqueous polyurethane is Lubrizol Corp. Sancure 777 type product, poly-second
Glycol monomethyl ether be Sigma-Aldrich, number-average molecular weight be the product of 1000.Above-mentioned subbing is coated extremely
The surface of interposing catheter, solidifies at 60 DEG C 1 hour, coats top coat paint to the conduit having been coated with subbing afterwards
On, solidify 1 hour at 80 DEG C, obtain outer surface and be coated with the conduit of cross-linked structure coating, then be dipped in dense ammonia
In water, at room temperature soak 1 hour, be dried 2 hours at 60 DEG C after taking-up, surface must be arrived there is Jie of Hydrophilic lubrication
Enter conduit.
Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit
It is 91.9% that wiping power reduces degree fp-r value, and it is 1.8% that the rubbed rear friction of conduit increases degree fp-i value.
Embodiment 4
Aqueous polyurethane, tetramethylolmethane-three (3-'-aziridino) propionic ester, deionized water are added to container, in room temperature
Lower stirring 30 minutes, obtains subbing, and wherein the quality of tetramethylolmethane-three (3-'-aziridino) propionic ester is the poly-ammonia of aqueous
The 3% of ester quality, the quality of deionized water is the 85% of subbing gross mass.Side carboxyl polyurethane CPU-3 will be contained, gather
Methyl vinyl ether-maleic acid, poly glycol monomethyl ether, N-Methyl pyrrolidone add to container, at room temperature
Stirring 30 minutes, obtain top coat paint, wherein CPU-3 is 1:1 with the mass ratio of polymethyl vinyl ether-maleic anhydride,
The quality of poly glycol monomethyl ether is the 5% of polymethyl vinyl ether-maleic anhydride quality, the quality of N-Methyl pyrrolidone
For top coat paint gross mass 85%.Polymethyl vinyl ether-maleic anhydride is Sigma-Aldrich, the equal molecule of number
Amount is the product of 80000, and aqueous polyurethane is Lubrizol Corp. Sancure 777 type product, and poly glycol monomethyl ether is
Sigma-Aldrich, number-average molecular weight are the product of 1000.Table by above-mentioned subbing coating to interposing catheter
Face, solidifies 1 hour, afterwards by top coat paint coating to the conduit having been coated with subbing, at 80 DEG C at 60 DEG C
Solidify 1 hour, obtain outer surface and be coated with the conduit of cross-linked structure coating, then be dipped in strong aqua ammonia, in room temperature
Lower immersion 1 hour, is dried 2 hours at 60 DEG C after taking-up, must arrive surface and have the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit
It is 92.2% that wiping power reduces degree fp-r value, and it is 1.9% that the rubbed rear friction of conduit increases degree fp-i value.
Embodiment 5
Aqueous polyurethane, trimethylolpropane-three [3-(2-methylaziridine base)] propionic ester, deionized water are added to holding
In device, it is stirred at room temperature 30 minutes, obtains subbing, wherein trimethylolpropane-three [3-(2-methylaziridine base)]
The quality of propionic ester is the 4% of aqueous polyurethane quality, and the quality of deionized water is the 87% of subbing gross mass.To contain
Side carboxyl polyurethane CPU-4, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, N, N-dimethyl sulfoxide
Add in container, be stirred at room temperature 30 minutes, obtain top coat paint, wherein CPU-4 and polymethyl vinyl ether-
The mass ratio of maleic anhydride is 1:2, and the quality of poly glycol monomethyl ether is polymethyl vinyl ether-maleic anhydride quality
The quality of 7%, N, N-dimethyl sulfoxide is the 87% of top coat paint gross mass.Polymethyl vinyl ether-maleic anhydride is west
Ge Ma aldrich company, number-average molecular weight are the product of 80000, and aqueous polyurethane is Lubrizol Corp. Sancure 777
Type product, poly glycol monomethyl ether be Sigma-Aldrich, number-average molecular weight be the product of 1000.By above-mentioned
Subbing coating, to the surface of interposing catheter, solidifies at 60 DEG C 1 hour, coats top coat paint to having been coated with afterwards
On the conduit of subbing, solidify 1 hour at 80 DEG C, obtain outer surface and be coated with the conduit of cross-linked structure coating, then
It is dipped in strong aqua ammonia, at room temperature soaks 1 hour, be dried 2 hours at 60 DEG C after taking-up, surface must be arrived and have
The interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit
It is 92.8% that wiping power reduces degree fp-r value, and it is 1.9% that the rubbed rear friction of conduit increases degree fp-i value.
Embodiment 6
Aqueous polyurethane, trimethylolpropane-three (3-'-aziridino) propionic ester, deionized water are added to container,
Stirring 30 minutes under room temperature, obtain subbing, wherein the quality of trimethylolpropane-three (3-'-aziridino) propionic ester is
The 5% of aqueous polyurethane quality, the quality of deionized water is the 90% of subbing gross mass.Side carboxyl polyurethane will be contained
CPU-5, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, ethyl acetate add to container, in room temperature
Lower stirring 30 minutes, obtains top coat paint, and wherein CPU-5 is 1:3 with the mass ratio of polymethyl vinyl ether-maleic anhydride,
The quality of poly glycol monomethyl ether is the 10% of polymethyl vinyl ether-maleic anhydride quality, and the quality of ethyl acetate is top layer
The 90% of coating gross mass.Polymethyl vinyl ether-maleic anhydride is that Sigma-Aldrich, number-average molecular weight are
The product of 80000, aqueous polyurethane is Lubrizol Corp. Sancure 777 type product, and poly glycol monomethyl ether is western lattice
Agate aldrich company, number-average molecular weight are the product of 1000.By the surface of above-mentioned subbing coating to interposing catheter,
Solidify at 60 DEG C 1 hour, afterwards by top coat paint coating to the conduit having been coated with subbing, at 80 DEG C, solidify 1
Hour, obtain outer surface and be coated with the conduit of cross-linked structure coating, then be dipped in strong aqua ammonia, at room temperature soak
1 hour, it is dried 2 hours at 60 DEG C after taking-up, surface must be arrived there is the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit
It is 92.9% that wiping power reduces degree fp-r value, and it is 1.8% that the rubbed rear friction of conduit increases degree fp-i value.
Embodiment 7
Aqueous polyurethane, tetramethylolmethane-three (3-'-aziridino) propionic ester, deionized water are added to container, in room temperature
Lower stirring 30 minutes, obtains subbing, and wherein the quality of tetramethylolmethane-three (3-'-aziridino) propionic ester is the poly-ammonia of aqueous
The 6% of ester quality, the quality of deionized water is the 92% of subbing gross mass.Side carboxyl polyurethane CPU-6 will be contained, gather
Methyl vinyl ether-maleic acid, poly glycol monomethyl ether, ethyl acetate add to container, are stirred at room temperature 30
Minute, obtain top coat paint, wherein CPU-6 is 1:4 with the mass ratio of polymethyl vinyl ether-maleic anhydride, poly-second two
The quality of alcohol monomethyl ether is the 12% of polymethyl vinyl ether-maleic anhydride quality, and the quality of ethyl acetate is that top coat paint is total
The 92% of quality.Polymethyl vinyl ether-maleic anhydride be Sigma-Aldrich, number-average molecular weight be 80000
Product, aqueous polyurethane is Lubrizol Corp. Sancure 777 type product, and poly glycol monomethyl ether is in Sigma's Order
Strange company, number-average molecular weight are the product of 1000.By the surface of above-mentioned subbing coating to interposing catheter, at 60 DEG C
Solidify 1 hour, afterwards by top coat paint coating to the conduit having been coated with subbing, solidify 1 hour at 80 DEG C,
It is coated with the conduit of cross-linked structure coating to outer surface, then is dipped in strong aqua ammonia, at room temperature soak 1 hour,
It is dried 2 hours at 60 DEG C after taking-up, surface must be arrived there is the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit
It is 93.2% that wiping power reduces degree fp-r value, and it is 1.8% that the rubbed rear friction of conduit increases degree fp-i value.
Embodiment 8
Aqueous polyurethane, trimethylolpropane-three [3-(2-methylaziridine base)] propionic ester, deionized water are added to holding
In device, it is stirred at room temperature 30 minutes, obtains subbing, wherein trimethylolpropane-three [3-(2-methylaziridine base)]
The quality of propionic ester is the 7% of aqueous polyurethane quality, and the quality of deionized water is the 94% of subbing gross mass.To contain
Side carboxyl polyurethane CPU-7, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, butyl acetate add extremely
In container, it is stirred at room temperature 30 minutes, obtains top coat paint, wherein CPU-7 and polymethyl vinyl ether-maleic acid
The mass ratio of acid anhydride is 1:5, and the quality of poly glycol monomethyl ether is the 14% of polymethyl vinyl ether-maleic anhydride quality, vinegar
The quality of acid butyl ester is the 94% of top coat paint gross mass.Polymethyl vinyl ether-maleic anhydride is that Sigma-Aldrich is public
Department, number-average molecular weight are the product of 80000, and aqueous polyurethane is Lubrizol Corp. Sancure 777 type product, poly-second
Glycol monomethyl ether be Sigma-Aldrich, number-average molecular weight be the product of 1000.Above-mentioned subbing is coated extremely
The surface of interposing catheter, solidifies at 60 DEG C 1 hour, coats top coat paint to the conduit having been coated with subbing afterwards
On, solidify 1 hour at 80 DEG C, obtain outer surface and be coated with the conduit of cross-linked structure coating, then be dipped in dense ammonia
In water, at room temperature soak 1 hour, be dried 2 hours at 60 DEG C after taking-up, surface must be arrived there is Jie of Hydrophilic lubrication
Enter conduit.
Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit
It is 93.5% that wiping power reduces degree fp-r value, and it is 1.9% that the rubbed rear friction of conduit increases degree fp-i value.
Embodiment 9
Aqueous polyurethane, trimethylolpropane-three (3-'-aziridino) propionic ester, deionized water are added to container,
Stirring 30 minutes under room temperature, obtain subbing, wherein the quality of trimethylolpropane-three (3-'-aziridino) propionic ester is
The 8% of aqueous polyurethane quality, the quality of deionized water is the 96% of subbing gross mass.Side carboxyl polyurethane will be contained
CPU-8, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, dichloromethane add to container, in room temperature
Lower stirring 30 minutes, obtains top coat paint, and wherein CPU-8 is 1:6 with the mass ratio of polymethyl vinyl ether-maleic anhydride,
The quality of poly glycol monomethyl ether is the 16% of polymethyl vinyl ether-maleic anhydride quality, and the quality of dichloromethane is top layer
The 96% of coating gross mass.Polymethyl vinyl ether-maleic anhydride is that Sigma-Aldrich, number-average molecular weight are
The product of 80000, aqueous polyurethane is Lubrizol Corp. Sancure 777 type product, and poly glycol monomethyl ether is western lattice
Agate aldrich company, number-average molecular weight are the product of 1000.By the surface of above-mentioned subbing coating to interposing catheter,
Solidify at 60 DEG C 1 hour, afterwards by top coat paint coating to the conduit having been coated with subbing, at 80 DEG C, solidify 1
Hour, obtain outer surface and be coated with the conduit of cross-linked structure coating, then be dipped in strong aqua ammonia, at room temperature soak
1 hour, it is dried 2 hours at 60 DEG C after taking-up, surface must be arrived there is the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit
It is 93.6% that wiping power reduces degree fp-r value, and it is 1.9% that the rubbed rear friction of conduit increases degree fp-i value.
Embodiment 10
Aqueous polyurethane, tetramethylolmethane-three (3-'-aziridino) propionic ester, deionized water are added to container, in room temperature
Lower stirring 30 minutes, obtains subbing, and wherein the quality of tetramethylolmethane-three (3-'-aziridino) propionic ester is the poly-ammonia of aqueous
The 9% of ester quality, the quality of deionized water is the 98% of subbing gross mass.Side carboxyl polyurethane CPU-6 will be contained, gather
Methyl vinyl ether-maleic acid, poly glycol monomethyl ether, chloroform add to container, are stirred at room temperature 30
Minute, obtain top coat paint, wherein CPU-6 is 1:7 with the mass ratio of polymethyl vinyl ether-maleic anhydride, poly-second two
The quality of alcohol monomethyl ether is the 18% of polymethyl vinyl ether-maleic anhydride quality, and the quality of chloroform is that top coat paint is total
The 98% of quality.Polymethyl vinyl ether-maleic anhydride be Sigma-Aldrich, number-average molecular weight be 80000
Product, aqueous polyurethane is Lubrizol Corp. Sancure 777 type product, and poly glycol monomethyl ether is in Sigma's Order
Strange company, number-average molecular weight are the product of 1000.By the surface of above-mentioned subbing coating to interposing catheter, at 60 DEG C
Solidify 1 hour, afterwards by top coat paint coating to the conduit having been coated with subbing, solidify 1 hour at 80 DEG C,
It is coated with the conduit of cross-linked structure coating to outer surface, then is dipped in strong aqua ammonia, at room temperature soak 1 hour,
It is dried 2 hours at 60 DEG C after taking-up, surface must be arrived there is the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit
It is 93.8% that wiping power reduces degree fp-r value, and it is 1.9% that the rubbed rear friction of conduit increases degree fp-i value.
Embodiment 11
Aqueous polyurethane, trimethylolpropane-three [3-(2-methylaziridine base)] propionic ester, deionized water are added to holding
In device, it is stirred at room temperature 30 minutes, obtains subbing, wherein trimethylolpropane-three [3-(2-methylaziridine base)]
The quality of propionic ester is the 10% of aqueous polyurethane quality, and the quality of deionized water is the 99% of subbing gross mass.Will
Add to holding containing side carboxyl polyurethane CPU-4, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, acetone
In device, it is stirred at room temperature 30 minutes, obtains top coat paint, wherein CPU-4 and polymethyl vinyl ether-maleic anhydride
Mass ratio be 1:10, the quality of poly glycol monomethyl ether is the 20% of polymethyl vinyl ether-maleic anhydride quality, acetone
Quality is top coat paint gross mass 99%.Polymethyl vinyl ether-maleic anhydride is Sigma-Aldrich, number
Average molecular weight is the product of 80000, and aqueous polyurethane is Lubrizol Corp. Sancure 777 type product, polyethyleneglycol
Methyl ether be Sigma-Aldrich, number-average molecular weight be the product of 1000.The coating of above-mentioned subbing is led to intervention
The surface of pipe, solidifies at 60 DEG C 1 hour, is coated to the conduit having been coated with subbing by top coat paint afterwards, in
Solidify 1 hour at 80 DEG C, obtain outer surface and be coated with the conduit of cross-linked structure coating, then be dipped in strong aqua ammonia,
At room temperature soak 1 hour, be dried 2 hours at 60 DEG C after taking-up, surface must be arrived there is the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit
It is 94.0% that wiping power reduces degree fp-r value, and it is 1.9% that the rubbed rear friction of conduit increases degree fp-i value.
Embodiment 12
By aqueous polyurethane, trimethylolpropane-three (3-'-aziridino) propionic ester, tetramethylolmethane-three (3-'-aziridino) third
Acid esters, deionized water add to container, are stirred at room temperature 30 minutes, obtain subbing, wherein trihydroxy methyl third
Quality is aqueous polyurethane quality the 2% of alkane-three (3-'-aziridino) propionic ester, tetramethylolmethane-three (3-'-aziridino) propanoic acid
The quality of ester is the 3% of aqueous polyurethane quality, and the quality of deionized water is the 90% of subbing gross mass.Side carboxylic will be contained
Based polyurethanes CPU-2, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, oxolane add to container
In, it is stirred at room temperature 30 minutes, obtains top coat paint, wherein CPU-2 and polymethyl vinyl ether-maleic anhydride
Mass ratio is 1:8, and the quality of poly glycol monomethyl ether is the 8% of polymethyl vinyl ether-maleic anhydride quality, oxolane
Quality is top coat paint gross mass 95%.Polymethyl vinyl ether-maleic anhydride is Sigma-Aldrich, number
Average molecular weight is the product of 80000, and aqueous polyurethane is Lubrizol Corp. Sancure 777 type product, polyethyleneglycol
Methyl ether be Sigma-Aldrich, number-average molecular weight be the product of 1000.The coating of above-mentioned subbing is led to intervention
The surface of pipe, solidifies at 60 DEG C 1 hour, is coated to the conduit having been coated with subbing by top coat paint afterwards, in
Solidify 1 hour at 80 DEG C, obtain outer surface and be coated with the conduit of cross-linked structure coating, then be dipped in strong aqua ammonia,
At room temperature soak 1 hour, be dried 2 hours at 60 DEG C after taking-up, surface must be arrived there is the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit
It is 93.6% that wiping power reduces degree fp-r value, and it is 1.8% that the rubbed rear friction of conduit increases degree fp-i value.
Embodiment 13
By aqueous polyurethane, trimethylolpropane-three [3-(2-methylaziridine base)] propionic ester, tetramethylolmethane-three (3-nitrogen third
Piperidinyl) propionic ester, deionized water add in container, be stirred at room temperature 30 minutes, obtain subbing, Qi Zhongsan
Quality is aqueous polyurethane quality the 4% of hydroxymethyl-propane-three [3-(2-methylaziridine base)] propionic ester, tetramethylolmethane-
Quality is aqueous polyurethane quality the 2% of three (3-'-aziridino) propionic ester, the quality of deionized water is the total matter of subbing
The 80% of amount.Side carboxyl polyurethane CPU-1, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, fourth will be contained
Ketone, oxolane add to container, are stirred at room temperature 30 minutes, obtain top coat paint, wherein CPU-1 and poly-first
The mass ratio of base vinyl ether-maleic acid is 1:9, and the quality of poly glycol monomethyl ether is polymethyl vinyl ether-maleic acid
The 6% of acid anhydride quality, the quality of butanone is the 40% of top coat paint gross mass, and the quality of oxolane is top coat paint gross mass
50%.Polymethyl vinyl ether-maleic anhydride be Sigma-Aldrich, number-average molecular weight be the product of 80000,
Aqueous polyurethane is Lubrizol Corp. Sancure 777 type product, and poly glycol monomethyl ether is that Sigma-Aldrich is public
Department, number-average molecular weight are the product of 1000.By the surface of above-mentioned subbing coating to interposing catheter, solidify at 60 DEG C
1 hour, afterwards by top coat paint coating to the conduit having been coated with subbing, solidify 1 hour at 80 DEG C, outside obtaining
Surface is coated with the conduit of cross-linked structure coating, then is dipped in strong aqua ammonia, at room temperature soaks 1 hour, takes out
After at 60 DEG C be dried 2 hours, surface must be arrived there is the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit
It is 93.1% that wiping power reduces degree fp-r value, and it is 1.7% that the rubbed rear friction of conduit increases degree fp-i value.
Claims (9)
1. the coating forming catheter surface hydrophilic coating, it is characterised in that coating comprises subbing and top layer is coated with
Material, described subbing is made up of aqueous polyurethane, polyfunctionality aziridine derivative and deionized water, the most officials
Quality is aqueous polyurethane quality 1%~the 10% of energy degree aziridine derivative, the quality of deionized water is that subbing is total
The 80%~99% of quality, described top coat paint is by containing side carboxyl polyurethane, polymethyl vinyl ether-maleic anhydride, poly-
Glycol monoethyl ether and organic solvent composition, wherein containing the matter of side carboxyl polyurethane with polymethyl vinyl ether-maleic anhydride
Amount ratio is 1:(0.1~10), the quality of poly glycol monomethyl ether is the 1%~20% of polymethyl vinyl ether-maleic anhydride quality,
The quality of organic solvent is the 80%~99% of top coat paint gross mass.
The coating of formation catheter surface hydrophilic coating the most according to claim 1, it is characterised in that described many officials
Energy degree aziridine derivative is trimethylolpropane-three [3-(2-methylaziridine base)] propionic ester, trimethylolpropane-three (3-
'-aziridino) propionic ester, one or more in tetramethylolmethane-three (3-'-aziridino) propionic ester.
The coating of formation catheter surface hydrophilic coating the most according to claim 1, it is characterised in that described containing side
The molecular chain structure of carboxyl polyurethane is by polyethers or polyester diol, diisocyanate, 2,2-dihydromethyl propionic acid and 1,4-
Butanediol is connected through additive reaction, and described polyethers or polyester diol are polyoxypropyleneglycol, PolyTHF two
One in alcohol, PCDL, polycaprolactone glycol, number-average molecular weight 1000~4000, two described isocyanides
Acid esters is 2,4 toluene diisocyanate, hexa-methylene 1,6-diisocyanate, 4,4'-methyl diphenylene diisocyanate, different
One in isophorone diisocyanate.
The coating of formation catheter surface hydrophilic coating the most according to claim 1, it is characterised in that described is organic
Solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, N, N-dimethyl sulfoxide,
One or more in ethyl acetate, butyl acetate, dichloromethane, chloroform, acetone, butanone, oxolane.
5. a preparation method for the coating of formation catheter surface hydrophilic coating according to claim 1, its feature exists
In, comprise the steps:
(1) preparation containing side carboxyl polyurethane: use solvent method synthesis polyurethane Han side carboxyl, by polyethers or polyester two
Unit's alcohol and diisocyanate add in reactor, are warming up to 80 DEG C, and stirring reaction obtained performed polymer after 1 hour, added 2,2-
Dihydromethyl propionic acid and BDO, after reacting 2 hours, add DMF, after continuing reaction 1 hour,
Add dibutyl tin laurate, then react 8 hours, be down to room temperature, solution in reactor is poured into equipped with deionized water
Container in, have white depositions to separate out, collect precipitate and be also washed with deionized 3 times, be positioned over vacuum drying and dry
In case, it is vacuum dried 48 hours at 90 DEG C, obtains transparent cake product, obtain after its pelletize containing side carboxyl polyurethane
Masterbatch, wherein, the molal quantity of described diisocyanate and polyethers or polyester diol, 2,2-dihydromethyl propionic acid and Isosorbide-5-Nitrae-
The ratio of the total mole number of butanediol is (1.05~1.2): 1,2,2-dihydromethyl propionic acid with the ratio of the molal quantity of BDO is
The quality of 1:1, polyethers or polyester diol and diisocyanate, 2,2-dihydromethyl propionic acid and the gross mass of BDO
Ratio be (1.5~1): 1, the quality of DMF is 4:1 with the ratio of the gross mass of other all raw materials, two Laurels
The quality of acid dibutyl tin is polyethers or the 1% of polyester diol quality, the quality of deionized water used and N, N-during precipitation
The mass ratio of dimethylformamide is 2:1, every time the quality of deionized water used and DMF during washing
Mass ratio be 2:1;
(2) preparation of subbing: aqueous polyurethane, polyfunctionality aziridine derivative, deionized water are added extremely
In container, being stirred at room temperature 30 minutes, obtain subbing, wherein the quality of polyfunctionality aziridine derivative is water
The 1%~10% of property polyurethane quality, the quality of deionized water is the 80%~99% of subbing gross mass;
(3) preparation of top coat paint: side carboxyl polyurethane, polymethyl vinyl ether-maleic anhydride, Polyethylene Glycol will be contained
Monomethyl ether, organic solvent add to container, are stirred at room temperature 30 minutes, obtain top coat paint, wherein containing side carboxyl
Polyurethane is 1:(0.1~10 with the mass ratio of polymethyl vinyl ether-maleic anhydride), the quality of poly glycol monomethyl ether is poly-
The 1%~20% of methyl vinyl ether-maleic acid quality, the quality of organic solvent is top coat paint gross mass
80%~99%.
The preparation method of the coating of formation catheter surface hydrophilic coating the most according to claim 5, it is characterised in that
Polyethers described in step (1) or polyester diol are polyoxypropyleneglycol, polytetrahydrofuran diol, Merlon
One in glycol, polycaprolactone glycol, number-average molecular weight is 1000~4000, and described diisocyanate is 2,4-toluene
Diisocyanate, hexa-methylene 1,6-diisocyanate, 4,4'-methyl diphenylene diisocyanate, isophorone two isocyanide
One in acid esters.
The preparation method of the coating of formation catheter surface hydrophilic coating the most according to claim 5, it is characterised in that
Polyfunctionality aziridine derivative described in step (2) is trimethylolpropane-three [3-(2-methylaziridine base)] propanoic acid
One in ester, trimethylolpropane-three (3-'-aziridino) propionic ester, tetramethylolmethane-three (3-'-aziridino) propionic ester or
Several.
The preparation method of the coating of formation catheter surface hydrophilic coating the most according to claim 5, it is characterised in that
Organic solvent described in step (3) is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-crassitude
Ketone, N, N-dimethyl sulfoxide, ethyl acetate, butyl acetate, dichloromethane, chloroform, acetone, butanone, tetrahydrochysene
One or more in furan.
9. a using method for the coating of formation catheter surface hydrophilic coating according to claim 1, its feature exists
In, comprise the steps:
(1) coating coating processing: by subbing by dip-coating, spray or brush in the way of coat the surface to conduit,
Solidify at 60 DEG C 1 hour, afterwards by top coat paint coating to the conduit having been coated with subbing, at 80 DEG C, solidify 1
Hour, obtain outer surface and be coated with the conduit of cross-linked structure coating;
(2) coating hydrophilic processes: is immersed to strong aqua ammonia by the conduit processed in step (1), at room temperature soaks
Steep 1 hour, be dried 2 hours at 60 DEG C after taking-up, surface must be arrived there is the interposing catheter of hydrophilic cross-linking structure coating.
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CN114276510A (en) * | 2022-02-09 | 2022-04-05 | 上海健倬生物科技有限公司 | Zero free amine isocyanate modified aziridine crosslinking agent, and preparation method and application thereof |
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