CN107929819A - A kind of medical metal surface hydrophilic coating and preparation method thereof - Google Patents
A kind of medical metal surface hydrophilic coating and preparation method thereof Download PDFInfo
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- CN107929819A CN107929819A CN201711181454.3A CN201711181454A CN107929819A CN 107929819 A CN107929819 A CN 107929819A CN 201711181454 A CN201711181454 A CN 201711181454A CN 107929819 A CN107929819 A CN 107929819A
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/10—Macromolecular materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/02—Inorganic materials
- A61L31/022—Metals or alloys
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/06—Coatings containing a mixture of two or more compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/08—Coatings comprising two or more layers
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Abstract
The present invention provides a kind of medical metal surface hydrophilic coating, including：It is arranged on the polymer elasticity precoated shet of the metal surface；It is arranged on the hydrophilic crosslinked layer of the polymer elasticity precoating layer surface；The hydrophilic crosslinked layer is formed by hydrophilic polymer, adhesive and crosslinking agent；Described adhesive is the polymer that can be reacted with hydrophilic polymer and crosslinking agent.Compared with prior art, the present invention first sets polymer elasticity precoated shet in metal surface, it can effectively ensure that metal hydrophilic coating in bending does not fall off, does not tear, do not influence the original compliance of metal with excellent ultra-thin elastic and adhesive property；At the same time, the present invention can be adjusted by the ratio of hydrophilic polymer and crosslinking agent in hydrophilic crosslinked layer, adjust the lubricity and cohesive force of hydrophilic crosslinked layer, and adhesive is added in hydrophilic crosslinked layer to form cross-linked network with hydrophilic polymer, reduce the amount that hydrophilic polymer is dissolved in water or blood, improve the persistence of hydrophilic coating.
Description
Technical field
The invention belongs to the field of medical instrument technology, more particularly to a kind of medical metal surface hydrophilic coating and its preparation side
Method.
Background technology
Endovascular Interventions technology is widely used in clinical vascular radiography, angioplasty, Intravascular Thrombus or foreign matter
Removing etc., it is not only easy to operate compared with traditional medical technology, but also since the wound of interventional treatment is low, can subtract
The pain of hypopathia people, Operative risk is smaller, and medical expense is relatively low, therefore this technology has obtained extensively in medical domain
Popularization and utilization.The medical instrument that current interventional therapy operation uses is mainly Group III medical instrument, its form mainly with
Based on medical treatment intervention high molecular material, medical treatment intervention wire and medical treatment intervention wire guide spring material.Medical treatment intervention is inorganic
It is special that the medical treatment intervention high molecular material of nonmetallic materials and medical treatment intervention composite material composition has that rigidity is low, passability is good etc.
Point, medical treatment intervention wire has the characteristics that intensity height, fatigue behaviour is good, good toughness and excellent processability, but
Need to use wire guide spring in some intervention operations, its good compliance and push performance preferably ensure that apparatus arrives
Reach and protect vascular tissue injury-free, such as radiography seal wire, guiding wire, puncture seal wire etc..
Medical treatment intervention wire guide spring is acted in human body, during being implanted into or intervening human body, is usually all
Friction reaction is directly contacted with organ or tissue's such as blood vessel of human body etc., therefore will to the performance of medical treatment intervention wire guide spring
Ask very high, except the raw material of medical treatment intervention wire guide spring, shape outside method, biologic medical intervenes the surface of alloy
The biocompatibilities such as state such as anti-hemolysis is hemagglutinin, antibiotic property and the hydrophilic and hydrophobic on surface are all particularly significant, this is related to people
Reaction of the body to the biologic medical intervention wire guide spring for being implanted into or intervening, such as mechanical damage, infection as caused by friction
Inflammation etc..Therefore, it is very necessary to be lubricated processing to medical treatment intervention metallized metal seal wire spring surface.
Hydrophilic coating is the effective means for improving medical treatment intervention metallized metal seal wire surface lubrication.Utilize hydrophilic coating pair
Medical treatment intervention wire guide spring surface is lubricated processing, when spring surface is contacted with tissue, produces the physics of complexity
Chemical action, can effectively reduce the rubbing action in insertion process.Coating also needs to note except to meet high hydrophilic lubrication performance
Weight greasy property firm and to stablize, coating will not fall off after being subjected to rubbing repeatedly, be subjected to spring alternating bending does not tear, and
Coating cannot influence the compliance feature that spring possesses in itself.
Patent at present on hydrophilic coating is relatively more, but is mainly applied to high molecular polymer surface such as Patent No.
The U.S. Patent Publication of US6042876, US4875287, US5509899, US5331027 and US5620738 is a kind of containing poly-
The hydrophilic coating of vinylpyrrolidone (PVP), two layers of coating point, but due to there is no introducing crosslinked structure in two layers of coatings, lead
Hydrophilic coating prepared by this method is caused to be easy to come off after water swelling, coating fastness is poor.And for example Patent No.
The U.S. Patent Publication of US4666437, US5179174, US8287890B2, US6299980B1 and US5160790 one kind is drawn
Enter the coating of crosslinking agent, crosslinking agent is isocyanates, as base coat, except containing PVP or polyoxyethylene in top coat
Outside the hydrophilic high mols such as alkene (PEO), the polyalcohol or polyamine that can be reacted with crosslinking agent are also added into, but due to parent
Water macromolecule is simultaneously not involved in the cross-linking reaction in system, by friction after water swelling, is still easy to take off from coated substrate
Fall.And for example Patent No. US8513320B2, US7534495B2, US 8039524B2, US 7696259B2, US8378011B2,
The United States Patent (USP) of US 8512795B2 discloses a kind of coating being solidified to form using ultraviolet light, including double bond compound and
Hydrophilic polymer, under the immixture of solvent, is evenly applied to equipment surfaces, then carries out ultraviolet light and cures to obtain crosslinking knot
Structure, but coating still has the problem of persistence after water swelling is bad.
Zhao Lei is in its doctor's thesis《The preparation and correlative study of novel hydrophilic coating coronary artery bracket》In elaborate
The method that metal support surface prepares hydrophilic coating, carries out hydroxylating using in stainless steel surface, then carries out silanization treatment,
Reacted from different silane coupling agents, so as to form the silane derivative for combining different hydrophilic group on coronary artery bracket surface
Material, but hydrophilic coating chance water can not form complete gel moisture film, not reach good lubricant effect.
The Chinese patent of Publication No. CN106634389A discloses the method for preparing hydrophilic coating in aluminium foil surface, but should
Method is used for air-conditioning heat-exchange fin aluminium foil surface, is not bio-medical level, and it is limited to meet water lubrication, it is impossible to meets to be situated between
Enter product requirement.The Chinese patent of Publication No. CN107213530A and CN107158484A disclose a kind of stainless steel
The preparation method of medical apparatus surface hydrophilic antimicrobial coatings, the surface for solving current medical instrument easily grow bacterium, cause
The problem of implant site superinfection, but in the coating and be not used crosslinking agent and sub- crosslinking agent, simple hydrophilic polymer with
Equipment surfaces combination power is limited, therefore cannot provide good coating persistence and slickness.
In conclusion domestic current hydrophilic coating is mainly used in polymeric surface, it is impossible to application very well
Metal material surface is intervened in medical treatment, especially produces hydrophilic coating in medical treatment intervention wire guide spring surface, its is submissive
Property, persistence, slickness and lear energy are undesirable.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of medical metal surface hydrophilic coating and its system
Preparation Method, the hydrophilic coating have preferable compliance, persistence and slickness.
The present invention provides a kind of medical metal surface hydrophilic coating, including：
It is arranged on the polymer elasticity precoated shet of the metal surface；
It is arranged on the hydrophilic crosslinked layer of the polymer elasticity precoating layer surface；The hydrophilic crosslinked layer is by hydrophilic polymer
Thing, adhesive and crosslinking agent are formed；Described adhesive is the polymer that can be reacted with hydrophilic polymer and crosslinking agent.
Preferably, the thickness of the polymer elasticity precoated shet is 0.005~0.01mm.
Preferably, the polymer elasticity precoated shet is by Parylene, phosphocholine polymer and polymethylacrylic acid
One or more formation in N-butyl.
Preferably, the thickness of the hydrophilic crosslinked layer is 0.005~0.01mm.
Preferably, the hydrophilic polymer is selected from polypropylene oxide, polyethers vinyl alcohol, polyethers ethyl acetate, polyethylene
One kind or more in base pyrrolidones, polyethylene oxide, carboxymethyl chitosan, polyvinyl alcohol, polyethylene glycol oxide and polyethylene glycol
Kind.
Preferably, described adhesive is polyurethane and/or its derivative.
Preferably, the crosslinking agent be selected from carbodiimides, aziridine compound, epoxy crosslinking agent, polyisocyanates with
One or more in type siloxane crosslinking agent.
Preferably, the mass ratio of the hydrophilic polymer and crosslinking agent is (10~100)：1.
Preferably, the mass ratio of the hydrophilic polymer and adhesive is (10~100):1.
Present invention also offers a kind of preparation method of medical metal surface hydrophilic coating, including：
S1 elastic polymer solution) is coated in metal surface, dry solidification forms polymer elasticity precoated shet；
S2 hydrophilic crosslinked layer solution) is formed into hydrophilic friendship coated in polymer elasticity precoating layer surface, dry solidification
Join layer；The hydrophilic crosslinked layer solution includes hydrophilic polymer, adhesive and crosslinking agent；Described adhesive for can with it is hydrophilic
Property polymer and crosslinking agent reaction polymer.
The present invention provides a kind of medical metal surface hydrophilic coating, including：It is arranged on the polymer of the metal surface
Elastic precoated shet；It is arranged on the hydrophilic crosslinked layer of the polymer elasticity precoating layer surface；The hydrophilic crosslinked layer is by hydrophily
Polymer, adhesive and crosslinking agent are formed；Described adhesive is the polymer that can be reacted with hydrophilic polymer and crosslinking agent.With
The prior art is compared, and the present invention first sets polymer elasticity precoated shet in metal surface, it is with excellent ultra-thin elastic with gluing
Performance is tied, can effectively ensure that metal hydrophilic coating in bending does not fall off, does not tear, do not influence the original compliance of metal；Together
When, the present invention can be adjusted by the ratio of hydrophilic polymer and crosslinking agent in hydrophilic crosslinked layer, adjust the profit of hydrophilic crosslinked layer
Slippery and cohesive force, and addition adhesive can form cross-linked network with hydrophilic polymer in hydrophilic crosslinked layer, reduce parent
Waterborne polymeric is dissolved in the amount of water or blood, improves the persistence of hydrophilic coating.
Brief description of the drawings
Fig. 1 is the structure diagram of medical metal surface hydrophilic coating provided by the invention；
Fig. 2 lubricates persistence test equipment photo for medical treatment intervention wire guide；
Fig. 3 is test sample photo；
Fig. 4 tests photo for sample compliance.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical solution in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, those of ordinary skill in the art's all other embodiments obtained without making creative work, all
Belong to the scope of protection of the invention.
The present invention provides a kind of medical metal surface hydrophilic coating, including：
It is arranged on the polymer elasticity precoated shet of the metal surface；
It is arranged on the hydrophilic crosslinked layer of the polymer elasticity precoating layer surface；The hydrophilic crosslinked layer is by hydrophilic polymer
Thing, adhesive and crosslinking agent are formed；Described adhesive is the polymer that can be reacted with hydrophilic polymer and crosslinking agent.
Referring to Fig. 1, Fig. 1 is the structure diagram of medical metal surface hydrophilic coating provided by the invention, wherein 1 is gold
Belong to, 2 be hydrophilic polymer, and 3 be adhesive, and 4 be crosslinking agent, and 5 be polymer elasticity precoated shet.
The metal is the metal well known to those skilled in the art for medical instrument, has no special limitation,
It is preferably medical treatment intervention wire guide in the present invention.
Medical metal surface hydrophilic coating provided by the invention includes the polymer elasticity precoated shet for being arranged on metal surface；
The thickness of the polymer elasticity precoated shet is preferably 0.005~0.01mm；The polymer elasticity precoated shet is by with elasticity
The polymer of property is formed, and the polymer with elastic property is polymer well known to those skilled in the art, and
Without special limitation；Preferably by Parylene, phosphocholine polymer and Vinalac 5920 in the present invention
One or more form polymer elasticity precoated shet.
The surface of the polymer elasticity precoated shet is provided with hydrophilic crosslinked layer；The thickness of the hydrophilic crosslinked layer is preferably
0.005~0.01mm；The hydrophilic crosslinked layer is formed by hydrophilic polymer, adhesive and crosslinking agent；The hydrophilic polymer
Thing is hydrophilic polymer well known to those skilled in the art, has no special limitation, is preferably polycyclic oxygen in the present invention
Propane, polyethers vinyl alcohol, polyethers ethyl acetate, polyvinylpyrrolidone, polyethylene oxide, carboxymethyl chitosan, polyethylene
One or more in alcohol, polyethylene glycol oxide and polyethylene glycol；The crosslinking agent is crosslinking agent well known to those skilled in the art
, special limitation is had no, is preferably carbodiimides, aziridine compound, epoxy crosslinking agent, polyisocyanic acid in the present invention
Ester and the one or more in type siloxane crosslinking agent；Described adhesive can be with hydrophilic polymer known to those skilled in the art
Thing and the polymer of crosslinking agent reaction, have no special limitation, are preferably polymerizeing comprising amino and carboxyl in the present invention
Thing, more preferably polyurethane and/or urethane derivative；The mass ratio of the hydrophilic polymer and crosslinking agent is preferably (10
~100)：1；The mass ratio of hydrophilic polymer and crosslinking agent is preferably 10 described in some embodiments provided by the invention：1；
In some embodiments provided by the invention, the mass ratio of the hydrophilic polymer and crosslinking agent is preferably 80：1；The present invention carries
In some embodiments supplied, the mass ratio of the hydrophilic polymer and crosslinking agent is preferably 20：1；It is provided by the invention another
In a little embodiments, the mass ratio of the hydrophilic polymer and crosslinking agent is preferably 100：1.The hydrophilic polymer and bonding
The mass ratio of agent is preferably (10~100)：1, more preferably (20~80)：1, it is further preferably (30~50)：1, it is further preferably (30
~40)：1, it is most preferably 30:1.In the present invention can by adjust the ratio of hydrophilic polymer, crosslinking agent and adhesive from
And adjust the lubricity and cohesive force of hydrophilic crosslinked layer.
Of the invention first to set polymer elasticity precoated shet in metal surface, it is with excellent ultra-thin elastic and caking property
Can, it can effectively ensure that metal hydrophilic coating in bending does not fall off, does not tear, do not influence the original compliance of metal；Meanwhile this
Invention can be adjusted by the ratio of hydrophilic polymer and crosslinking agent in hydrophilic crosslinked layer, adjust the lubricity of hydrophilic crosslinked layer with
Cohesive force, and addition adhesive can form cross-linked network with hydrophilic polymer in hydrophilic crosslinked layer, reduce hydrophily and gather
Compound is dissolved in the amount of water or blood, improves the persistence of hydrophilic coating.
Present invention also offers a kind of preparation method of above-mentioned medical metal surface hydrophilic coating, including：S1 it is) that elasticity is poly-
Polymer solution is coated in metal surface, and dry solidification forms polymer elasticity precoated shet；S2) hydrophilic crosslinked layer solution is coated in
The polymer elasticity precoats layer surface, and dry solidification forms hydrophilic crosslinked layer；The hydrophilic crosslinked layer solution includes hydrophilic
Property polymer, adhesive and crosslinking agent；Described adhesive is the polymer that can be reacted with hydrophilic polymer and crosslinking agent.
Wherein, the present invention is not particularly limited the source of all raw materials, is commercially available.
The polymer elasticity precoated shet is same as above with hydrophilic coating, and details are not described herein.
Elastic polymer solution is coated in metal surface, dry solidification forms polymer elasticity precoated shet；The elasticity
The concentration of solvent is preferably 0.005~0.5g/ml in polymer solution, more preferably 0.01~0.5g/ml, is further preferably 0.05
~0.3g/ml, is most preferably 0.05~0.1g/ml；Solvent in the elastic polymer solution is ripe for those skilled in the art
The solvent known, has no special limitation, is preferably acetone, ethyl acetate, chloroform, toluene, dimethylbenzene, diformazan in the present invention
Base formamide (DMF) and the one or more in tetrahydrofuran (THF)；The method of the coating is known to those skilled in the art
Method, have no special limitation, be preferably dip-coating, spraying or smearing in the present invention；The temperature of the dry solidification is excellent
Elect 50 DEG C~150 DEG C as, more preferably 60 DEG C~130 DEG C, be further preferably 90 DEG C~120 DEG C；The time of the dry solidification is excellent
Elect 10min~2h as, more preferably 0.5~2h, be further preferably 1~2h.
By hydrophilic crosslinked layer solution coated in polymer elasticity precoating layer surface, dry solidification forms hydrophilic crosslinked
Layer；The hydrophilic crosslinked layer solution includes hydrophilic polymer, adhesive and crosslinking agent；Described adhesive is can be with hydrophily
Polymer and the polymer of crosslinking agent reaction；The hydrophilic polymer, adhesive and crosslinking agent are same as above, herein no longer
Repeat.In the present invention, the hydrophilic crosslinked layer solution is preferably prepared according to following steps：Prepare binder solution；Then will be viscous
Mixture solution is added into the solution of hydrophilic compounds, is eventually adding crosslinking agent, is stirred evenly, and it is molten to obtain hydrophilic crosslinked layer
Liquid.The concentration of adhesive is preferably 5~30wt% in described adhesive solution；Solvent in described adhesive solution is this area
Solvent known to technical staff, has no special limitation, be preferably in the present invention acetone, ethyl acetate, chloroform, toluene,
Dimethylbenzene, dimethylformamide (DMF) and the one or more in tetrahydrofuran (THF)；In the hydrophilic polymer solution
The concentration of hydrophilic polymer is preferably 2~10wt%；Solvent in the hydrophilic polymer solution is people in the art
Solvent known to member, has no special limitation, be preferably in the present invention ethyl acetate, diacetone alcohol, dimethylformamide,
Butanone and the one or more in glycerine.The mode of the coating for mode well known to those skilled in the art, and
It is preferably dip-coating, spraying or smearing in the present invention without special limitation；The temperature of the dry solidification is preferably 50 DEG C~150
DEG C, more preferably 60 DEG C~130 DEG C, be further preferably 60 DEG C~100 DEG C；The time of the dry solidification is preferably 10min~2h,
More preferably 10~60min, is further preferably 30~60min.
According to the present invention, according to the requirement of medical metal surface hydrophilic coating smoothness, the hydrophilic crosslinked layer of coating is repeated
The step of solution and dry solidification.
The preparation method of medical metal surface hydrophilic coating provided by the invention is easy to operate, and cost is low, the parent prepared
Water coating has lasting lubricity, good biocompatibility, good compliance and excellent tear resistance.
In order to further illustrate the present invention, with reference to embodiments to a kind of medical metal surface hydrophilic provided by the invention
Coating and preparation method thereof is described in detail.
Reagent used is commercially available in following embodiments.
Embodiment 1
1.1 prepare the ethyl acetate elastic polymer solution that Vinalac 5920 content is 0.1g/ml.
Elastic polymer solution described in step 1.1 is coated uniformly on medical treatment intervention metal by 1.2 with the mode of spraying
Seal wire spring surface, 90 DEG C of drying 2h, is formed by curing polymer elasticity precoated shet (thickness 0.005mm).
The polyurethane solutions that 1.3 preparation solutes contents are 5wt% are as sub- adhesive (solvent is tetrahydrofuran).
1.4 the polyurethane solutions are added to hydrophilic radical polyvinylpyrrolidone solution (3wt%, it is molten
Agent is ethyl acetate, diacetone alcohol, and the mass ratio of polyvinylpyrrolidone and polyurethane is 30：1) 1h, is stirred, adds carbon
Changing diimine crosslinking agent, (mass ratio of polyvinylpyrrolidone and carbodiimide cross-linker is 10:1) 2h, is stirred, is obtained
Hydrophilic crosslinked layer solution A.
Hydrophilic coating solution A in 1.5 steps 1.4 is coated uniformly on polymer elasticity precoating layer surface, in 60 DEG C of height
The lower baking and curing 30min of temperature, forms the hydrophilic crosslinked layer (thickness 0.005mm) of first layer.
It can continue following steps as needed：
1.6 mass ratioes for changing the step the polyvinylpyrrolidone solution and carbodiimide cross-linker in 1.4 are 80:
1,1h is stirred, forms hydrophilic crosslinked layer B solution.
Hydrophilic crosslinked layer B solution in 1.7 steps 1.6 is coated uniformly on first hydrophilic crosslinked layer of table after step 1.5
Face, the baking and curing 30min under 60 DEG C of high temperature, forms the hydrophilic crosslinked layer (thickness 0.005mm) of the second layer.
Experimental result shows that the medical treatment coated with hydrophilic coating prepared according to above-mentioned steps intervenes wire guide spring table
Face, lubricity improves 75% and coating has good persistence, and spring bending coating comes off without tear, nothing, and coating
The compliance of spring in itself is not influenced.
Medical treatment intervention wire guide lubrication persistence test method：
Test equipment has constant temperature water tank, sink, digital display dynamometer, friction testing frock, fixes sheath in the sink
Connector, the wire guide of test sample 0.025 ", test sample is fixed on digital display dynamometer with fixture, keep sample and
In the same horizontal line, it is 300mm/min to adjust dynamometer speed to friction testing frock, and measuring distance is ± 50mm, every time
Digital display dynamometer is zeroed before test, and each sample slidably reciprocates 50 times, and value of thrust is before the good each pulling force coating of record
24.5g, the 1st time test pulling force be 5.6g, and it is 6.5g that the 50th time, which is tested pulling force, is differed very with the 1st testing friction power for the 50th time
It is small, illustrate that coating has good persistence；Test average tension value is 8.2g after forming the first hydrophilic coating, forms the second parent
Average tension value is in 6.1g after water coating.
Fig. 2 lubricates persistence test equipment photo for medical treatment intervention wire guide；Fig. 3 is test sample photo, and Fig. 4 is sample
Product compliance tests photo.
Embodiment 2
2.1 prepare the toluene elastic polymer solution that Parylene content is 0.05g/ml.
Elastic polymer solution described in step 2.1 is coated uniformly on medical treatment intervention metal by 2.2 with the mode of dip-coating
Seal wire spring surface, 120 DEG C of drying 1h, is formed by curing polymer elasticity precoated shet (thickness 0.005mm).
2.3 prepare polyurethane solutions of the solutes content for 30wt% as sub- adhesive (solvent dimethylformamide).
2.4 are added to the polyurethane solutions polyglycol solution (concentration 5wt% and solvent two with hydrophilic radical
Pyruvic alcohol, butanone；The mass ratio of polyethylene glycol and polyurethane is 30:1) 1h, is stirred, adds isophorone diisocyanate friendship
Joining agent, (polyethylene glycol is 20 with isoflurane chalcone diisocyanate crosslinking agent quality ratio:1) 0.5h, is stirred, obtains hydrophilic crosslinked layer A
Solution.
Hydrophilic crosslinked layer solution A in 2.5 steps 2.4 is coated uniformly on polymer elasticity precoating layer surface, at 60 DEG C
Baking and curing 30min under high temperature, forms the hydrophilic crosslinked layer (thickness 0.005mm) of first layer.
It can continue step as needed：
2.6 mass ratioes for changing the step polyglycol solution and isophorone diisocyanate crosslinking agent in 2.5 are
100:1,0.5h is stirred, forms hydrophilic crosslinked layer B solution.
Hydrophilic coating B solution in 2.7 steps 2.6 is coated uniformly on the first hydrophilic coating surface after step 2.5,
Baking and curing 30min under 60 DEG C of high temperature, forms the hydrophilic crosslinked layer (thickness 0.005mm) of the second layer.
Test method is as in the first embodiment, experimental result is shown, according to the gold coated with hydrophilic coating of above-mentioned steps preparation
Metal surface, lubricity improves 79% and coating has good persistence, and spring bending coating comes off without tear, nothing, and
Coating does not influence the compliance of spring in itself：Test sample head end bends to designated position, head end branch before elastic precoated shet
Support force is 0.331g, is 0.338g after elastic precoated shet, is 0.351g after the setting hydrophilic crosslinked layer of the second layer.
Claims (10)
- A kind of 1. medical metal surface hydrophilic coating, it is characterised in that including：It is arranged on the polymer elasticity precoated shet of the metal surface；It is arranged on the hydrophilic crosslinked layer of the polymer elasticity precoating layer surface；The hydrophilic crosslinked layer by hydrophilic polymer, Adhesive is formed with crosslinking agent；Described adhesive is the polymer that can be reacted with hydrophilic polymer and crosslinking agent.
- 2. medical metal surface hydrophilic coating according to claim 1, it is characterised in that the polymer elasticity precoated shet Thickness be 0.005~0.01mm.
- 3. medical metal surface hydrophilic coating according to claim 1, it is characterised in that the polymer elasticity precoated shet Formed by Parylene, phosphocholine polymer and the one or more in Vinalac 5920.
- 4. medical metal surface hydrophilic coating according to claim 1, it is characterised in that the thickness of the hydrophilic crosslinked layer For 0.005~0.01mm.
- 5. medical metal surface hydrophilic coating according to claim 1, it is characterised in that the hydrophilic polymer is selected from Polypropylene oxide, polyethers vinyl alcohol, polyethers ethyl acetate, polyvinylpyrrolidone, polyethylene oxide, carboxymethyl chitosan, One or more in polyvinyl alcohol, polyethylene glycol oxide and polyethylene glycol.
- 6. medical metal surface hydrophilic coating according to claim 1, it is characterised in that described adhesive is polyurethane And/or its derivative.
- 7. medical metal surface hydrophilic coating according to claim 1, it is characterised in that the crosslinking agent is selected from carbonization two One or more in imines, aziridine compound, epoxy crosslinking agent, polyisocyanates and type siloxane crosslinking agent.
- 8. medical metal surface hydrophilic coating according to claim 1, it is characterised in that the hydrophilic polymer is with handing over The mass ratio for joining agent is (10~100)：1.
- 9. medical metal surface hydrophilic coating according to claim 1, it is characterised in that the hydrophilic polymer is with gluing The mass ratio of mixture is (10~100)：1.
- A kind of 10. preparation method of medical metal surface hydrophilic coating, it is characterised in that including：S1 elastic polymer solution) is coated in metal surface, dry solidification forms polymer elasticity precoated shet；S2 hydrophilic crosslinked layer solution) is formed into hydrophilic crosslinked layer coated in polymer elasticity precoating layer surface, dry solidification； The hydrophilic crosslinked layer solution includes hydrophilic polymer, adhesive and crosslinking agent；Described adhesive is that can gather with hydrophily Compound and the polymer of crosslinking agent reaction.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111744055A (en) * | 2020-06-29 | 2020-10-09 | 北京星云中御科技有限公司 | Hydrophilic implant product and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999044668A1 (en) * | 1998-03-04 | 1999-09-10 | C.R. Bard, Inc. | Flexible, kink resistant, low friction guidewire with formable tip, and method for making same |
| CN101812265A (en) * | 2009-02-24 | 2010-08-25 | 赛诺医疗科学技术有限公司 | Hydrophilic coat solution applied to surface of medicinal instrument and preparation method thereof |
| CN105268085A (en) * | 2015-11-10 | 2016-01-27 | 深圳麦普奇医疗科技有限公司 | Hydrophilic micro-guide wire for minimally-invasive intervention and manufacturing method of hydrophilic micro-guide wire |
| CN105268084A (en) * | 2015-11-10 | 2016-01-27 | 深圳麦普奇医疗科技有限公司 | Guide wire applicable to clinical intravascular interventional therapy and manufacturing method of guide wire |
| CN106955411A (en) * | 2017-04-10 | 2017-07-18 | 深圳麦普奇医疗科技有限公司 | A kind of new uropoiesis and digestive endoscope zebra superslide seal wire |
-
2017
- 2017-11-23 CN CN201711181454.3A patent/CN107929819B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999044668A1 (en) * | 1998-03-04 | 1999-09-10 | C.R. Bard, Inc. | Flexible, kink resistant, low friction guidewire with formable tip, and method for making same |
| CN101812265A (en) * | 2009-02-24 | 2010-08-25 | 赛诺医疗科学技术有限公司 | Hydrophilic coat solution applied to surface of medicinal instrument and preparation method thereof |
| CN105268085A (en) * | 2015-11-10 | 2016-01-27 | 深圳麦普奇医疗科技有限公司 | Hydrophilic micro-guide wire for minimally-invasive intervention and manufacturing method of hydrophilic micro-guide wire |
| CN105268084A (en) * | 2015-11-10 | 2016-01-27 | 深圳麦普奇医疗科技有限公司 | Guide wire applicable to clinical intravascular interventional therapy and manufacturing method of guide wire |
| CN106955411A (en) * | 2017-04-10 | 2017-07-18 | 深圳麦普奇医疗科技有限公司 | A kind of new uropoiesis and digestive endoscope zebra superslide seal wire |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111744055A (en) * | 2020-06-29 | 2020-10-09 | 北京星云中御科技有限公司 | Hydrophilic implant product and preparation method thereof |
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