Medical apparatus surface coating and application
Technical field
The invention belongs to medical instruments field, and in particular to medical apparatus surface coating and application.
Background technology
Medical lubricant coating has relatively low skin-friction coefficient coated in medical apparatus surface, such as seal wire, PTCA conduits,
Catheter, endoscope etc., when insertion is with extracting, the friction of apparatus and body tissue is reduced, mitigates the pain of patient in art,
Doctor's operating difficulties, diseased region is cannot be introduced into because frictional resistance is big in face of harsh lesion.
In the prior art, table of the interventional medical apparatus under blood and organizational environment is reduced by coating lubricant coating
Face coefficient of friction, relatively effective mode is to carry out surface treatment to interventional medical apparatus to form hydrophilic coating, described hydrophilic
Coating aquation can form one layer of water-swellable gel rapidly in aqueous environment, be largely water in this water-swellable layer,
Liquid barrier is formed between apparatus and tissue, because fluid molecule Interaction Force is weaker, is appointed by eliminating in motion process
What solid directly shows to contact with solid, so as to significantly reduce the friction between surface and surface, alleviates to people
The damage of body tissue, and bring great convenience for interventional therapy operation operation.
For example patent US4119094 is mentioned using the mixed solution of solvent-based polyisocyanate and polyurethane as bottom substrates,
Contain unreacted isocyanate groups in solution, using the solution of polyvinylpyrrolidone as Topcoating solution, dry, 65 degree
Solidify 6 hours.Patent US4373009, patent EP0106004B1, using polyisocyanate ester solution as bottom substrates layer, its
In include unreacted isocyanate group, use can with isocyanates formed Covalent bonding together hydrophile copolymers for top painting
Layer.Solvent-based thermal plastic polyurethane and polyvinylpyrrolidone blend coating solution are used in patent US4642267, is applied
Afterwards, solidification obtains.
The coating mentioned in above-mentioned patent, it is hydrophilic common by the way that the top of Covalent bonding together can be formed with isocyanates
Polymers can firmly be attached to interventional medical equipment surfaces, but the reactivity of isocyanates is higher, and solution is not easy
Preserve, need to have used in a short time with postponing, be unsuitable in industrialized production, can only small lot use, low production efficiency
Under.
The content of the invention
The invention provides a kind of medical apparatus surface coating and application, is used to solve current medical apparatus surface
Paint stability is poor, the problem of being not easy industrial applications.
In order to solve the above-mentioned technical problem, the technical scheme is that:The medical apparatus surface coating, including parent
Waterborne polymeric, polyhydroxylated polymer, anhydrides crosslinking agent and decentralized medium, the polyhydroxylated polymer can including at least two
It is crosslinked terminal hydroxy group.
The hydrophilic polymer refers to (such as hydroxyl, carboxyl, amido and polyethylene oxide chain containing multiple hydrophilic radicals
Section) polymer, these polymer may be dissolved in water in the presence of hydrophilic radical.
Wherein, hydrophilic polymer is that coating forms main body;Polyhydroxylated polymer and the reaction of anhydrides crosslinking agent, after reaction
Product can cause whole coating to form crosslinking inierpeneirating network structure, hydrophilic polymer is attached to medical apparatus surface.
Further, the polyhydroxylated polymer is selected from cellulose and its derivates, hyperbranched polyol polyester, hyperbranched
Polyhydroxy polycarboxylic carboxylic acid amide esters, one or more of hyperbranched polyhydroxy polycarboxylic urethane and castor oil.
Further, the anhydrides crosslinking agent is selected from maleic anhydride, itaconic anhydride, succinic anhydride or dodecyl
One or more in succinic anhydride and polystyrene-maleic anhydride copolymer.
Further, the hydrophilic polymer is selected from polyethylene pyrrole network alkanone, polyoxyethylene or polyamide.
Further, the one kind of the decentralized medium in ethyl acetate, chloroform, dichloromethane, methanol, second alcohol and water
More than, preferred alcohol, water or ethanol water.
Further, the medical apparatus surface is as follows by weight percentage with coating each component:
Further, the percentage by weight of each component is as follows:
Present invention also offers a kind of forming method of coating, comprise the following steps:
Hydrophilic polymer, polyhydroxylated polymer, anhydrides crosslinking agent, decentralized medium are put into container, are mixed into homogeneous
Solution is completed after solution to prepare.The solution is imposed on into the medical apparatus surface by spraying, infiltrating or brush, is put into baking oven
At 90-130 DEG C, coating preparation is completed after solidifying 30-60 minutes.
Present invention also offers a kind of medicine equipment, the medical apparatus surface is attached with above-mentioned medical apparatus surface and applied
Material.
Present invention also offers a kind of hydrophilic coating of medical apparatus surface, the hydrophilic coating include waterborne polymeric,
Polyhydroxylated polymer and anhydrides crosslinking agent.
Technical scheme provided by the invention is to form hydrophilic polymer and alkyd cross-linked polymer in medical apparatus surface
IPN, in liquid environment, lubricity, at least one characteristic of fastness increase the coating of formation, because anhydrides are handed over
It is appropriate to join agent activity, therefore system is relatively stable, is adapted to industrial operation and preservation, compared with prior art, 20 frictions are real
After testing, lubricity does not substantially reduce, and performance does not substantially change after storage for a long time.
Embodiment
With reference to specific embodiment, technical scheme is expanded on further.It should be understood that these embodiments are only used for
Illustrate the present invention rather than limitation the scope of the present invention.The experimental method of unreceipted actual conditions in the following example, generally
According to normal condition, or according to the condition proposed by manufacturer, the reagent in unreceipted source is purchased in market in the following example
Commodity.
Medicine equipment involved in the present invention can be the apparatus or extracorporeal device to implant.The apparatus can be temporary in short term
When use, it is or long-term permanent implanted.In some embodiments, suitable apparatus is that those are generally used for losing for the rhythm of the heart
Tune, heart failure, valvular disease, angiosis, diabetes, sacred disease and deficiency disorder, plastic surgery, neurosurgery, tumour
Learn, ophthalmology and ENT operations provide medical treatment and/or the apparatus diagnosed.Medicine equipment involved in the present invention includes but is not limited to
Following equipment:Support, stent graft, the connector that coincide, synthesis paster, lead, electrode, pin, wire, conduit, sensor, hand
Art instrument, angiopoiesis ball, wound drain, isocon (shunt), pipe, transfusion cover simple (infusion sleeve), urine
Road intubation, bead, implant, blood oxygenation generator, pump, vascular graft, flush type intervention medicine box (vascular
Access port), heart valve, annuloplasty ring, suture, surgical clips, operation nail, artificial or electronic heart pacemaker, implantable defibrillator,
Nerve stimulator, plastic surgery apparatus, celiolymph isocon, implantable Teat pipette, vertebra cage, artificial intervertebral disc, the replacement of nucleus pulposus
Apparatus, syrinx, intra-ocular lens and any pipe used in Minimally Invasive Surgery.
Coating involved in the present invention can be combined by kinds of processes with the surface of medicine equipment, as dip-coating, spraying,
Washing, gaseous phase deposition, brushing, roller coat and other methods known in the art.
Coating involved in the present invention can be controlled in several ways when medicine equipment is combined to form hydrophilic coating
The thickness of coating processed:Change soak time, change pulling speed or change the viscosity and applying step of Hydrophilic coating formulation
Number.
The material of medical apparatus surface involved in the present invention can be that high polymer material can also be metal or alloy material
Material.The preferably copolymer of polyether sulfone, polyurethane, silicone, polyester, polyamide, polyethers, polyolefin and above-mentioned polymer.
The present invention discloses a kind of medical apparatus surface coating composition, and said composition includes:(1) hydrophilic polymer,
Such as polyethylene pyrrole network alkanone, polyoxyethylene, polyamide;(2) it is the polymer at least containing two hydroxyls containing general structure, it is such as fine
Tie up plain, hyperbranched polyhydroxylated polymer, castor oil etc.;(3) polymer containing general structure for acid anhydrides, such as maleic anhydride,
The polymer such as itaconic anhydride, succinic anhydride, dodecyl succinic anhydride.The coating composition forms master with hydrophilic polymer
Body, comprising hydrophilic radical be soluble in water or there are good water absorbing properties.General structure for acid anhydrides material and
General structure is that at least the polymer containing two hydroxyls is reactant, and it is mutual can make it that whole coating forms crosslinking for product after reaction
Network structure is worn, hydrophilic polymer is attached to medical apparatus surface.Solution each component is very stable, is not easy to react, molten
Liquid is easy to preserve.
The invention also discloses a kind of hydrophilic coating prepared by aforementioned coating composition, the hydrophilic coating can be by above-mentioned
Composition is coated in matrix surface after being sufficiently mixed with liquid medium, and hydrophilic coating is formed after solidification.
Hydrophilic coating forming method includes:Above-mentioned composition is placed in container.Liquid medium is added into said vesse,
Liquid medium can be ethanol or the mixture of water or second alcohol and water, ethyl acetate, chloroform, dichloromethane.Treat the group in container
After compound forms uniform solution with liquid medium, by solution spraying to matrix surface.Heating said solution, obtain being formed at matrix
The hydrophilic coating on surface.
Embodiment 1
The medical apparatus surface is as follows with coating 200mL each component:
Said components are well mixed in a reservoir, preserved stand-by.
Coating and curing are:The medical apparatus surface of embodiment 1 is sprayed on sample with coating, be heating and curing temperature
Spend for 90 DEG C, heat time 30min.
Comparative example 1
Coating and curing are:The medical apparatus surface of comparative example 1 is sprayed on sample with coating, be heating and curing temperature
Spend for 90 DEG C, heat time 30min.
Contrast experiment
After embodiment 1 and comparative example 1 are deposited into 1 month, 12 months and 24 months, by coating and curing in pebax
Coating is formed on sample, then carries out the test of 1 frictional force and 20 frictional force, to assess lubricated with coating after long-term storage
Whether have an impact with performance in terms of fastness, as a result as shown in table 1, the coating of embodiment 1 performance after the storage of 24 months
Without significant change, and the lubricity of embodiment 1 increases compared with comparative example 1, and 20 times frictional force does not also substantially rise, explanation
Coating is directly firmly bonded degree height, excellent durability with matrix.
Table 1 is the experimental data of lubricity and fastness after long-term storage:
Embodiment 2
The medical apparatus surface is as follows with coating 200mL each component:
Said components are well mixed in a reservoir, normal temperature preserves stand-by.Solution after above-mentioned storage 12 months is placed in
In tube-type receptacle, medical polyurethane (PU) material conduit will be intervened and immerse solution after 30 seconds, with 5cm/min speed from solution
Middle proposition, be put into 100 DEG C of curing oven 40min, obtain the conduit with hydrophilic coating, to conduit in water 1 frictional force and
20 friction testings, as shown in table 2.Storage 12 months after, coating for matrix still have extraordinary being firmly bonded property and
Greasy property.
Table 2 is the experimental data of the pipe friction power test of embodiment 2:
Particle test is carried out to the conduit for scribbling embodiment 2, significant change does not occur for coated microgranules, it was demonstrated that coating and conduit
It is firmly combined with, coating is still effective, and experimental data is shown in Table 3.
Table 3 is the experimental data of the conduit particle test of embodiment 2
|
Particle number (number) |
Coating rear tube (can be tested) |
1560 |
Coating rear tube (after December) |
1620 |
Embodiment 3
The medical apparatus surface is as follows with coating 200mL each component:
Said components are well mixed in a reservoir, preserved stand-by.
Coating and curing are:The medical apparatus surface of embodiment 3 is sprayed on sample with coating, be heating and curing temperature
Spend for 130 DEG C, heat time 1h.To conduit in water 1 frictional force and 20 friction testings, as shown in table 4, storage 12
After individual month, coating still has extraordinary being firmly bonded property and greasy property for matrix.
Table 4 is the experimental data of the pipe friction power test of embodiment 3:
Particle test (can with place 12 months after) is carried out to product after above-mentioned coating, coated microgranules do not occur substantially to become
Change, it was demonstrated that coating is still effective, and experimental result is shown in Table 5.
Table 5 is the experimental data of the conduit particle test of embodiment 3:
|
Particle number (number) |
Coating rear tube (can be tested) |
1706 |
Coating rear tube (placing 12 months)) |
1810 |
Embodiment 4
The medical apparatus surface is as follows with coating 200mL each component:
Said components are well mixed in a reservoir, normal temperature preserves stand-by.
Solution after above-mentioned storage 12 months is placed in tube-type receptacle, medical polyurethane (PU) material conduit will be intervened
Solution is immersed after 30 seconds, is proposed with 5cm/min speed from solution, is put into 100 DEG C of curing oven 40min, is obtained with parent
The conduit of water coating, to conduit in water 1 frictional force and 20 friction testings, as shown in table 6, storage 12 months after, apply
Material still has extraordinary being firmly bonded property and greasy property for matrix.
Table 6 is the experimental data of the pipe friction power test of embodiment 4:
Particle test (at once with place 12 months after) is carried out to product after above-mentioned coating, coated microgranules do not occur substantially to become
Change, it was demonstrated that coating is still effective, and experimental result is shown in Table 7.
Table 7 is the experimental data of the conduit particle test of embodiment 4:
|
Particle number (number) |
Coating rear tube (is tested) at once |
1706 |
Coating rear tube (placing 12 months)) |
1810 |
Embodiment 5
The medical apparatus surface is as follows with coating 200mL each component:
Said components are well mixed in a reservoir, normal temperature preserves stand-by.
Solution after above-mentioned storage 12 months is placed in tube-type receptacle, medical polyurethane (PU) material conduit will be intervened
Solution is immersed after 30 seconds, is proposed with 5cm/min speed from solution, is put into 100 DEG C of curing oven 40min, is obtained with parent
The conduit of water coating, to conduit in water 1 frictional force and 20 friction testings, as shown in table 8, storage 12 months after, apply
Material still has extraordinary being firmly bonded property and greasy property for matrix.
Table 8 is the experimental data of the pipe friction power test of embodiment 5:
Particle test (at once with place 12 months after) is carried out to product after above-mentioned coating, coated microgranules do not occur substantially to become
Change, it was demonstrated that coating is still effective, and experimental result is shown in Table 9.
Table 9 is the experimental data of the conduit particle test of embodiment 5:
|
Particle number (number) |
Coating rear tube (is tested) at once |
1706 |
Coating rear tube (placing 12 months)) |
1810 |
Embodiment 6
The medical apparatus surface is as follows with coating 200mL each component:
Said components are well mixed in a reservoir, normal temperature preserves stand-by.
Solution after above-mentioned storage 12 months is placed in tube-type receptacle, medical polyurethane (PU) material conduit will be intervened
Solution is immersed after 30 seconds, is proposed with 5cm/min speed from solution, is put into 100 DEG C of curing oven 40min, is obtained with parent
The conduit of water coating, to conduit in water 1 frictional force and 20 friction testings, as shown in table 10, storage 12 months after, apply
Material still has extraordinary being firmly bonded property and greasy property for matrix.
Table 10 is the experimental data of the pipe friction power test of embodiment 6
Particle test (at once with place 12 months after) is carried out to product after above-mentioned coating, coated microgranules do not occur substantially to become
Change, it was demonstrated that coating is still effective, and experimental result is shown in Table 11.
Table 11 is the experimental data of the conduit particle test of embodiment 6
|
Particle number (number) |
Coating rear tube (is tested) at once |
1540 |
Coating rear tube (placing 12 months)) |
1350 |
Embodiment 7
The medical apparatus surface is as follows with coating 200mL each component:
Said components are well mixed in a reservoir, normal temperature preserves stand-by.
Solution after above-mentioned storage 12 months is placed in tube-type receptacle, medical polyurethane (PU) material conduit will be intervened
Solution is immersed after 30 seconds, is proposed with 5cm/min speed from solution, is put into 100 DEG C of curing oven 40min, is obtained with parent
The conduit of water coating, to conduit in water 1 frictional force and 20 friction testings, as shown in table 12, storage 12 months after, apply
Material still has extraordinary being firmly bonded property and greasy property for matrix.
Table 12 is the experimental data of the pipe friction power test of embodiment 7:
Particle test (at once with place 12 months after) is carried out to product after above-mentioned coating, coated microgranules do not occur substantially to become
Change, it was demonstrated that coating is still effective, and experimental result is shown in Table 11.
Table 13 is the experimental data of the conduit particle test of embodiment 7:
|
Particle number (number) |
Coating rear tube (is tested) at once |
1460 |
Coating rear tube (is placed 12 months) |
1521 |
Technical scheme stable system provided by the invention, polyhydroxylated polymer and anhydride polymer have good stabilization
Property, functional group's torpescence is not susceptible to react in normal temperature, easily stored, is adapted to industrial operation and preservation.With prior art phase
Than having lubricity good, lubricity and fastness substantially do not change after storing for a long time.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not limited to the substantial technological content model of the present invention
Enclose, substantial technological content of the invention is broadly to be defined in the right of application, any technology that other people complete
Entity or method, if with the right of application defined in it is identical, also or a kind of equivalent change, will
It is considered as being covered by among the right.