WO2011093542A1 - Actionneur polymère, cathéter contenant celui-ci et procédé de préparation de l'actionneur polymère - Google Patents

Actionneur polymère, cathéter contenant celui-ci et procédé de préparation de l'actionneur polymère Download PDF

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Publication number
WO2011093542A1
WO2011093542A1 PCT/KR2010/000534 KR2010000534W WO2011093542A1 WO 2011093542 A1 WO2011093542 A1 WO 2011093542A1 KR 2010000534 W KR2010000534 W KR 2010000534W WO 2011093542 A1 WO2011093542 A1 WO 2011093542A1
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Prior art keywords
polymer
ion exchange
driving
electrode
combinations
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PCT/KR2010/000534
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English (en)
Korean (ko)
Inventor
한문희
조재영
이계한
이장열
왕혁식
윤벼리
Original Assignee
서울대학교 산학협력단
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Priority to PCT/KR2010/000534 priority Critical patent/WO2011093542A1/fr
Publication of WO2011093542A1 publication Critical patent/WO2011093542A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M25/00—Catheters; Hollow probes
    • A61M25/01—Introducing, guiding, advancing, emplacing or holding catheters
    • A61M25/0105—Steering means as part of the catheter or advancing means; Markers for positioning
    • 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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/04—Macromolecular materials
    • 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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M25/00—Catheters; Hollow probes
    • A61M25/01—Introducing, guiding, advancing, emplacing or holding catheters
    • A61M25/09—Guide wires
    • A61M25/09041—Mechanisms for insertion of guide wires
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M25/00—Catheters; Hollow probes
    • A61M25/0043—Catheters; Hollow probes characterised by structural features
    • A61M2025/0058—Catheters; Hollow probes characterised by structural features having an electroactive polymer material, e.g. for steering purposes, for control of flexibility, for locking, for opening or closing

Definitions

  • the present invention provides a polymer driving body comprising a plurality of electrode coating layers present on a part of (i) the electrically conductive polymer laminate and ( ⁇ ) the surface of the lamp assembly, a manufacturing method thereof, and controlling the driving characteristics of the polymer driving body.
  • a catheter comprising a method and a polymer driver.
  • the catheter represents a thin tube or tube, which is used as a bypass for the urethra and esophagus, used to discharge the contents or to inject drugs, or to the heart or cerebrovascular vessels through blood vessels such as arteries. It is used for infusion of therapeutic devices, infusion of angiographic agents and removal of blood clots.
  • active catheters are the latter, aimed at performing certain surgical operations where they need to be examined or treated safely and quickly through complex and narrow pathways such as blood vessels.
  • the micro memory When injecting the catheter into the body, there is a risk of entering the unwanted direction at the vascular bifurcation or damaging the vascular wall.
  • SMA shape memory alloy
  • Multi-degree of freedom drive mechanism and sensor using a sieve (actuator) Attempts have been made to mount the catheter tip.
  • the study of active catheter to safely move the catheter to a certain place is one of the important techniques for minimally invasive surgery. This is the main research topic among researchers currently dealing with MEMS and microdrives. Most of these active catheters are predominantly technical techniques for the design of the mechanical operating part, in this case, the size of the operating part is large, there is a problem that can not operate in micro-vascular such as cerebrovascular.
  • shape memory alloy when used as an active catheter's driving body, deformation and recovery should occur between 49-52 ° C and 37 ° C, which is the minimum temperature that damages the tissues of skin or blood vessels.
  • the shape memory alloy that can be deformed at this temperature is the only alloy in which a small amount of third metal such as vanadium, crumb, manganese, and cobalt is added to the nickel-titanium alloy (Ni-Ti alloy), but the price of the raw material is high. The price has a high disadvantage.
  • the deformation temperature of shape memory alloy is very sensitive to the change of composition ratio.
  • the materials presented include shape memory alloys, superelastic alloy tubes and fluids, micro valves and balloons, and guide wires equipped with pressure sensors and ultrasonic probes. Most of them are confined to shape memory alloys and have limitations in clinical applications.
  • the polymer driving body has recently attracted attention as a next-generation driving device that can realize artificial muscle, and the polymer driving body has characteristics such as large strain rate, low driving pressure, softness and low density (light weight), so that it can be applied as an active catheter. It has the disadvantage of small generating force, low rigidity, low responsiveness, and low durability.
  • the polymer driving body is deformed by external stimulation such as electricity, chemistry, heat, light and magnetism, but the most practical one is the driving device by electrical stimulation.
  • Ionic Conducting Polymer Film (ICPF) actuators exhibit high-speed bending behavior when voltage is applied to the platinum layer electrodes on both sides of Nafion.
  • the present invention provides a polymer comprising (i) a light emitting electroactive polymer laminate and ( ⁇ ) a plurality of electrode coating layers present on a part of the surface of the light emitting laminate.
  • a catheter comprising a driving body and a polymer driving body is presented.
  • the present invention relates to an isotropic stack of electroactive polymers selected from ionic polymers, conductive polymers, carbon nanotubes, dielectric polymers, electrostrictive polymers, nanoclays, silica compounds, and combinations thereof
  • the present invention relates to a polymer driving body including a plurality of electrode coating layers present on a part of the surface of a laminate, wherein the driving characteristics are improved, as well as the ion exchange capacity of the ion groups present in the electroactive polymer, the number of silver groups, the distribution of the ion groups, and the relative cation. It is possible to adjust the driving characteristics by controlling at least one selected from the type of, the thickness of the ion exchange membrane, and the surface electrode thickness.
  • the present invention is a polymer that enables improvement and control of driving characteristics by a series of processes including an ion exchange membrane lamination step of a plurality of electroactive polymers, a pretreatment step of heating, a thermocompression step, an electrode coating step, and an insulating layer forming step.
  • the present invention (i) gideung type electroactive polymer laminate, and ( ⁇ ) gideung the stacked electrodes includes a plurality of the coating layer present on a portion of the water surface, the catheter polymer actuator ⁇ i for which it is characterized.
  • the present invention (b) laminating a plurality of electroactive polymer ion exchange membrane, (c) heating the laminated ion exchange membrane at 170-190 ° C for 10-20 minutes, (d) the heated Thermally compressing the ion exchange membrane at 6,500-7,000 psi and 170-190 ° C. for 10-20 minutes, (e) the thermally compressed
  • the present invention (b ') laminating a second exchange membrane so that a duct forming light is present between the plurality of ion-exchange membrane between the plurality of electroactive polymer ion exchange membrane, (c) the stacked ion exchange membrane 170- Heating at 190 X for 10-20 minutes; (d) thermocompressing the heated ion exchange membrane at 6,500-7,000 psi and 10-20 minutes at 170-190 ° C., (e ') of an isotropic stack.
  • thermo-compressed ion exchange membrane such that an inner duct is present in the longitudinal direction and removing the duct- like lamps to obtain a lamp stack, (h) coating an electrode on the surface of the lamp trap; And, (i) there is another feature in the method of manufacturing a polymer drive comprising the step of forming an insulating layer by removing a portion of the electrode coating layer.
  • the present invention is a catheter comprising a polymer driving body according to system 3, the driving force of 0.2 gi or more, the driving displacement of 40 ° or more, the strength of 8 X 1 7 Nra 2 or more, the density less than 0.25 g / cm 3 and 2.0
  • the catheter is used as a guidewire for catheter insertion or as an active catheter for device or drug injection. There is another feature of the catheter.
  • the present invention also relates to a columnar laminate of electroactive polymers selected from (i) ionic polymers, conductive polymers, carbon nanolevers, dielectric polymers, electrostrictive polymers, nanoclays, silica compounds, and combinations thereof. And ( ⁇ ) a polymer driving body comprising a plurality of electrode coating layers selected from platinum, gold, silver, copper, nickel, lead, cadmium, and alloys thereof present on a portion of the surface of the lamp body.
  • the polymer driving body and the catheter using the same according to the present invention can be smoothly adjusted by electric stimulation with high practicality, and it is possible to improve driving characteristics such as driving displacement, driving force, and strength, and to adjust driving characteristics so that the desired position in the blood vessel can be determined.
  • Fluorescence combined with the catheter and the imaging probe as well as the catheter for surgery and treatment with the improvement of the success rate of vascular treatment, reduction of complications, stability of the procedure and universalization of cerebrovascular diseases such as cerebral aneurysm. Its expectation is expected in the field of imaging.
  • Figure 1 shows a SEM photograph of the cross section (a) and shape (b, c) of the etc. of the shaped laminate prepared in Example 1-1 of the present invention.
  • Figure 2 shows the SEM image of the surface before (a) and after the coating (b) before the electrode coating on the surface of the light-emitting laminate prepared in Example 1-1 of the present invention.
  • the present invention zones (i) the electrically conductive polymer laminates, and ( ⁇ ) the etc.
  • the present invention is characterized by a polymer drive comprising (i) a luminescent electroactive polymer laminate and ( ⁇ ) a plurality of electrode coating layers present on a portion of the surface of the luminescent laminate.
  • the electroactive polymer forming the shaped laminate may be selected from ionic polymers, conductive polymers, carbon nanotubes, dielectric polymers, electrostrictive polymers, nanoclays, silica compounds, and combinations thereof.
  • the 'combination' includes both the above two kinds and a copolymer or a molten phase, or a liquid blend, a molten phase or a liquid or solid mixture of the two or more substances, and a combination thereof.
  • the ionic polymer is a fluorine-based polymer in which at least one selected from a sulfonic acid group and a carbonyl group and an ionic group are introduced, for example
  • One or a combination of two or more selected from- (CF 2 CF 2 )-(CF 2 CF) -and Cf: 3 may be used, and as one example, a fluorine-based group having a sulfonic acid group introduced into an anion group
  • Nafion8 containing O-CF ⁇ FiCF ⁇ OCF ⁇ F 2 can be used.
  • the conductive polymer may be selected from polyaniline, polypyrrole, polysulfone, polyacetylene, and combinations thereof
  • the dielectric polymer may be selected from polyacrylate, silicone, pulley vinylidene fluoride, and combinations thereof.
  • the electrostrained polymer may be selected from polyacrylates, silicones, polyurethanes, and combinations thereof, and nanoclays may be used in which one or more ionic groups selected from sulfonated and carbonyl groups are introduced.
  • the silver group of the nanoclay is generally used in the art and is not particularly limited.
  • the present invention uses a method of controlling the amount of silver group by irradiating gamma rays, but is not limited thereto.
  • the silica compound may use silica monomers modified through sulfonation or carbonylation and their superpolymers.
  • the conductive polymer, the carbon nano-lever, the dielectric polymer, the electrostrictive polymer, the nanoclay, the silica compound, etc. used as the electroactive polymer cause the swelling change by various physical and chemical changes. By the change, the driving performance is improved.
  • Conductive polymers have a volume change caused by the sequencing / extraction of hydrated ions during their oxidation / reduction process [J.
  • volume change is induced [Science, 1999, 284, 1340]; Dielectric polymers induce a volume change through the rearrangement of induced polarization molecules when a strong electric field is applied, especially when the acrylic polymer is tensioned before driving Much larger size changes are induced [Science, 2000, 287, 836]; electrostrained polymers exhibit changes in molecular structure under strong electric fields with a volumetric deformation of about 4% [Scifence, 1998, 836, 2101].
  • an oxide of a plate transition metal such as vanadium, which may be additionally used between the light emitting stack and the electrode coating layer, causes hydration of hydrates in the interlayer structure, causing volume change, and thus driving.
  • a plate transition metal such as vanadium
  • the driving force is improved.
  • a method of preparing a sieve, or manufacturing a polymer driving body with one kind of electroactive polymer and then coating another kind of electroactive polymer on the surface of the manufactured polymer driving body may be used.
  • a method of preparing a membrane using a solution phase mixture may be a three-dimensional constant casting method, which is generally used in the art, and the coating method may be a method in which another electroactive polymer is coated on the upper surface of one electroactive polymer.
  • a method of impregnating and coprecipitation in a polymer solution and then polymerizing on the surface is also possible.
  • Such column stacks can have a variety of shapes, in particular
  • the columnar laminate may be prepared by thermocompression bonding an electroactive polymer having a thickness of 175-185) to a final thickness of 900-1100 / an.
  • the final thickness of the electroactive polymer is less than 900 im, it may be difficult to use the catheter's driving body due to the reduction of the driving force. If the final thickness of the electroactive polymer exceeds 1100, the driving speed and displacement are significantly reduced due to the increase of its rigidity. Due to the problem that can not be inserted into the blood vessel can occur.
  • Electrode coating layer formed by coating on the surface of the light-emitting laminate is in the art although not particularly limited to those used, specifically, one selected from platinum, gold, copper, nickel, lead, cadmium, and alloys thereof may be used.
  • platinum is used as a metal for forming the electrode coating layer, but nickel, lead, copper, and silver are used for forming the electrode or [J. Electroanal. Chem., 1993, 360,
  • the electrode coating layer is present on a part of the surface of the light emitting stack, and is continuously or intermittently positioned in the longitudinal direction of the light stack.
  • the degree of freedom of the electrode is determined by the number of planes.
  • the electrode can not be used because it is rarely used. For example, for the entire surface area of an isotropic reptile with a square cross section,
  • the continuous electrode layer in the longitudinal direction of the stack
  • the electrode layer may be formed intermittently in the longitudinal direction by coating the electrode layer in the intermediate direction in the longitudinal direction of the laminate, or by removing the electrode layer having a predetermined thickness in the longitudinal direction of the electrode layer coated on the entire surface of the laminate. It is also possible to obtain an electrode layer formed intermittently in the direction.
  • the electrode layer is formed on a total of four surfaces to have four degrees of freedom.
  • the polymer driving body of the present invention may further include (iii) an internal duct existing in the longitudinal direction of the latticed stack, and the cross section of the duct may be selected in shape according to the intended use, and is not particularly limited. Do not.
  • the duct has a cross section with a long axis of 0.2-0.5 mm 3, and it is preferable that the ratio (D: d) of the long axis D of the cross section of the elongated laminate and the long axis d of the duct is 1: 0.2-0.5.
  • the long axis of the duct is less than 0.2 mm it may be difficult to administer the drug, if it exceeds 0.5 ⁇ , the thickness of the structure around the duct is reduced, there is a problem that can be cracked or broken when driving the polymer drive, and also If the ratio (D: d) of the long axis (D) of the cross section of the mold stack to the long axis (d) of the duct is less than 1: 0.2, it may be difficult to inject the instrument and drugs, and if it exceeds 1: 0.5, Problems can occur that cause breakage of the etc. stack.
  • the duct when used for the treatment of an aneurysm, it is desirable to secure a long axis of 0.2 mm or more so that the platinum coil can be inserted and a long axis of 0.2 mm or less when the duct is used for thrombolytic drug injection.
  • 'long axis' means the longest distance between two arbitrary points on the figure. For example, if the shape is a circle, the long axis is the diameter, the longest diagonal line, and the long axis corresponds to the ellipse.
  • the polymer driving body of the present invention may further include (iv) a single layer or two or more mixed layers selected from conductive polymers, carbon nanotubes, and transition metal oxides between the lamp stack and the electrode coating layer.
  • the conductive polymer, carbon nano-lube, transition metal oxide and inorganic particles in the art Although generally used is not particularly limited, specifically, the conductive polymer may be a polyaniline, polypyri, polysulfone or polyacetylene selected from the group consisting of one or two or more, and the transition metal oxide is a transition metal such as vanadium Oxides may be used.
  • These additionally included layers are formed using dip coating, layer by layer self-assembly, spin coating: atomic layer deposition sputtering, electropolymerization and chemical polymerization, which are commonly used in the art, and consider the effect on driving performance. Maintain a 10-200 IM thickness range.
  • (V) may further include at least one layer selected from silicon-based, polyurethane-based, parylene-based and epoxy-based coating layers present on the electrode coating layer. This layer is present not only on the electrode layer but also on the name between the electrode layers serving as the insulating layer.
  • the silicone-based, polyurethane-based, parylene bran [Smart Mater.
  • the coating layer formed of the cured epoxy resin improves the blocking force between the polymer driving body and the external tissues to improve the biocompatibility and blood compatibility. It is possible to secure.
  • the coating layer is also formed in the coating layer using the dip coating, thermal evaporation method, thermosetting method commonly used in the art, and maintains the thickness range of 1-3 ⁇ in consideration of the effect on the driving performance.
  • the polymer driving body according to the present invention preferably has a driving force of 0.1 g f or more, preferably 0.1-0.2 g f , a driving displacement of 40 ° or more, preferably 4 ° 90 ° , and an intensity of 8 X 10 "7 Nm 2 or more.
  • a driving force of 0.1 g f or more, preferably 0.1-0.2 g f
  • a driving displacement of 40 ° or more, preferably 4 ° 90 °
  • an intensity of 8 X 10 "7 Nm 2 or more For example, 1 X 10— 6 -5.2 ⁇ 10 "6 Nm 2 , the response speed is less than 2.0 mm / s, preferably 1.0-2.0 ⁇ / s, and the density is less than 0.3 g / cm 3, preferably 0.20-0.25. It is advisable to maintain the g / cm 3 range.
  • the range suggested by the factor representing the driving characteristics of the polymer driving body of the present invention means a degree capable of performing a role as the driving body, specifically, the driving characteristics are 'above', 'less',' less than ", But this The lower limit or the upper limit of the range is limited to the extent to which the role of the driving body in the art can be performed.
  • the present invention relates to (i) an isotropic stack of electroactive polymers selected from ionic polymers, conductive polymers, carbon nanolevers, dielectric polymers, electrostrictive polymers, nanoclays, silica compounds and combinations thereof, and
  • the electroactive polymer for a polymer driving body comprising a plurality of electrode coating layers selected from platinum, gold, silver, copper, nickel, lead, cadmium, and alloys thereof present on a portion of the surface of the lamp body;
  • a polymer driving body comprising a plurality of electrode coating layers selected from platinum, gold, silver, copper, nickel, lead, cadmium, and alloys thereof present on a portion of the surface of the lamp body;
  • the surface resistance continues to decrease, which plays a positive role in driving performance.
  • the driving force decreases due to an increase in the rigidity of the electrode itself.
  • the driving performance is different depending on the type of cation that can move inside, the larger the size of the hydrated cation, the driving displacement and driving force increases.
  • the present invention manufactures a polymer drive by using a lamination method of a film, in particular a lamination method by thermocompression bonding.
  • the lamination method by thermocompression is possible to form a uniform thickness as well as to secure the desired physical properties, it is easy to reproduce the square shape difficult to implement in various shapes, especially liquid casting method in a simple method.
  • a method of laminating membranes is widely known in addition to thermocompression bonding, such as casting of a liquid phase and adhesion between commercially available ion exchange membranes.
  • Method for producing a polymer driving body (b) laminating a plurality of electroactive polymer ion exchange membrane, (c) heating the laminated ion exchange membrane at 170-190 ° C for 10-20 minutes Step, (d) thermocompressing the heated ion exchange membrane at 6,500-7,000 psi and 170-190 1C ' for 10-20 minutes; (e) cutting the thermocompressed ion exchange membrane to obtain an etc. laminate And (h) coating an electrode on the surface of the lamp stack, and (i) forming an insulating layer by partially removing the electrode coating layer.
  • a plurality of electroactive polymer ion exchange membranes are laminated.
  • a silver exchange membrane so that the duct forming lamp is present between the plurality of electroactive polymer ion exchange membrane.
  • the duct forming lamp is not particularly limited as long as it is capable of forming a duct. Specifically, the shape of the duct is small and the deformation is maintained under the conditions of high pressure and high pressure of 6500-7000 psi and 170-190. It is possible to use a wire structure capable of maintaining the diameter and having various cross-sectional shapes.
  • metal wires such as wires, copper wires, and lead wires can be used. It is performed by, but is not limited thereto.
  • This stacking preferably forms the same number of ion exchange membranes on the surface of the guide lamp, so as to have the same thickness from the duct.
  • the laminating may be performed before laminating the electroactive polymer ion exchange membrane.
  • the washing is performed to remove dust, and when fine dust remains on the surface, it inhibits the formation of uniform and excellent electrodes, thereby preventing problems in catheter performance. There is a possibility to cause it.
  • This cleaning may be generally used for non-polar organic solvent such as n- nucleic acid used to perform the degree specifically 1-5 times or more times, in the related art.
  • thermocompression furnace is generally used in the art of the stainless steel bar, by controlling the thickness of the bar it is possible to control the thickness of the lamp laminate of the present invention.
  • the thickness of the mold is preferably maintained to 75-85% with respect to the thickness of the laminated electroactive polymer ion exchange membrane.
  • the fluidity of the membrane interface is improved by the heating pretreatment process, and the conditions thereof are appropriate conditions under which the fluidity of the internal structure is ensured through the experiment of the thermal properties of the ion exchange membrane and the functional groups are not destroyed.
  • the ion exchange membrane is melted or the interface between the surface and the membrane may burn.
  • the time is less than 10 minutes, the ion exchange membrane may not adhere, and if it exceeds 20 minutes, the surface-membrane interface may burn out.
  • the heated ion exchange membrane is thermocompressed at 6,500-7,000 psi and 170-190 ° C. for 10-20 minutes.
  • the compressive force between the remarkably low may not adhere to the ion exchange membrane
  • the thickness of the ion exchange membrane may be uneven or burned.
  • the time is less than 10 minutes, the ion-exchange membrane may not adhere, and if it exceeds 20 minutes, burning may occur, so it is preferable to maintain the above range.
  • the removal of impurities is specifically from 60-100 ° C for 5-6 hours the hydrogen peroxide cleaning hajeong, 90-120 ° C 3-4 It is carried out in a series of processes including washing the aqueous solution for 3 hours, washing the aqueous hydrochloric acid solution for 3-4 hours at 60-100 C, and washing the aqueous solution for 3-4 hours at 90-120 ° C.
  • the hydrogen peroxide and hydrochloric acid solution is preferably maintained at a concentration of 5-15% by weight.
  • Coating of the electrode forms an electrode coating layer on the surface of the etc. laminate using the electroless plating method commonly used in the art.
  • the electroless plating may be performed under a mixed solvent in which water and alcohol maintain a weight ratio of 100: 8-30.
  • each single solvent such as water and alcohol commonly used in the art is used.
  • the volume increase rate of the ion exchange membrane is increased and the interface state between the electrode and the ion exchange membrane is improved, which contributes to the improvement of driving characteristics such as driving speed, driving displacement and response speed of the manufactured polymer driving body. .
  • the driving performance is increased than when using a single solvent of water, but the driving performance of the present invention may not be satisfied, and when the amount of alcohol used exceeds 30 weight ratio It is preferable to maintain the above range because a problem of separation of the thermally laminated film may occur.
  • Alcohol is in the field of sugar
  • alcohols having 1 to 6 carbon atoms specifically methanol, ethanol, isopropanol, butanol, pentanol and nucleic acidol, preferably ethanol and methane, and more preferably ethane.
  • the thickness of the electrode coated by the above method is in the range of 10-30 /, preferably in the range of 20-30 fM. If the thickness range is less than 10, the electrode may be unevenly formed so that the driving performance may be degraded or may not be driven. And 30 When exceeding, it is preferable to maintain the above range because a problem that driving performance may be degraded due to the rigidity of the electrode occurs.
  • the insulating layer forming method may be performed using cutting, scratching, taping, and masking, which are generally used in the art, wherein the insulating layer has a thickness of 5-15 urn in a direction opposite to the length thereof, preferably 7-12 im. Two to eight, preferably four.
  • the present invention is a catheter comprising the polymer drive as described above, preferably 0.1 g f or more, preferably 0, 1-0.2 gf drive force, 40 ° or more drive displacement of 40-90 °, 8 10 "7 Nm 2 or more preferably 1 x 10 _6 -5.2 x 10 "6 Nm 2 strength and less than 2.0 mm / s preferably 1.0-2.0 mm / s
  • a catheter having a stepping speed and a diameter of 1.5 kPa or less, preferably in the range of 1.5-1 kPa, wherein the catheter is used as a gimwire for catheter insertion or as an active catheter for instrument or drug injection.
  • the drug is more suitable for use for thrombolysis using thrombolytics.
  • the catheter including the polymer drive device according to the present invention is located on the surface or inside the catheter distal end, locally injected drugs such as thrombolytics, or the catheter distal end
  • Such a catheter is not particularly limited to one having a structure and a design generally used in the art, but specifically, an active type connected to an end of a tube after bonding an electrode to a polymer driving body having an luminescent structure having a duct for drug administration therein.
  • Catheter structure, or guide wire structure that controls the direction of the tube by pushing another delivery catheter in the tube [IEEE International Conference on Robotics and Automat ion, 79, 1995].
  • Nafion (180 mm thick) was cut to a size of 24 mm 49 mm, and then the surface was cleaned with n-nucleic acid to remove dust on the surface of Nafion. Laminating six sheets of Nafion membranes whose surface was treated, and during the lamination
  • Lamination was carried out by inserting a wire 0.5 mm in diameter between the third and fourth.
  • the membrane was covered with a polyimide film having a characteristic of 50 (M thickness, heat resistance, etc. from above and below, and then placed in a stainless steel frame (25 mm .width X 50 mm length X 0.93 mm height.
  • the size of the Nafion membrane can be adjusted by placing the mold on a hot-press and leaving it under pressure for about 12 minutes at about 180 ° C to destroy the functionalities of the membrane's internal structure. Under conditions
  • the laminated napi was first stored in an aqueous solution for about 1 hour to remove impurities from the membrane. Afterwards, to get rid of the messy things on the four sides, cut the four sides with a knife to make a rectangular shape. Remove the wire contained inside the napi silver film and 10% by weight of about 60 x:
  • an electrode coating layer of platinum on the surface of the lampshade laminate, first, a solvent mixture of 100: 30 weight ratio of water and ethanol in which [Pt (NH 3 ) 4 ] 2 Cl 2 platinum salt is dissolved at a concentration of 2 mg / ral was impregnated with an ion exchange membrane. After 24 hours of impregnation, the ion exchange membrane was stirred at 100 rpm under a temperature of 40 ° C, and electroless plating was performed under the condition that 5 ml of NaBH 4 5 wt% mixed solvent was added 10 times every 30 minutes. In this case, the electrode coating layers are continuously positioned, and six are present in the opposite plane of the lamp stack.
  • Example 1-2 Change of Electroactive Polymer Type
  • Example 1 In order to apply to Example 1, a composite was prepared using a mixture of carbon nanotubes and a solution in which an ionic polymer membrane was peeled off. Nafion aqueous solution and carbon nanotubes were mixed in a 100: 15 weight ratio and stirred for 62 hours. After the 3D constant casting method. Membranes were prepared at a thickness within 180 where the thickness uniformity was maintained. At this time, the three-dimensional constant casting was carried out while evaporating the solvent within 5 hours in the 60 ° C silver range, in the process, the carbon nanotubes and Nafion solution was formed a complex film forming a uniform film. Since the lamination and electrode coating process was performed in the same process as in Example 1.
  • Example 1-3 Change of Electroactive Polymer Type
  • Example 2 Proceed in the same manner as in Example 1, in order to introduce the conductive polymer, Nafion lamp obtained after the manufacture of the lamp-shaped structure was impregnated with 0.07 M of blood in an aqueous solution for 5 minutes. Thereafter, the polypyrrole was polymerized near the surface by impregnation with 20 wt% hydrogen peroxide. The conductive polymer composite obtained through this process was repeatedly washed with 0.7 M sulfuric acid, nitric acid, and water at room temperature and high temperature (60 ° C) for 1 hour interval. Since the prepared composite is subjected to the electrode coating process the same as in Example 1
  • Example 1-4 Type change of electroactive polymer
  • Example 1-5 Type change of electroactive polymer
  • Example 1-6 Type change of electroactive polymer
  • a polymer driving body was prepared in the same manner as in Example 1-1, using nanoclay having a sulfonation group having a thickness of 180 urn instead of Nafion.
  • Example 1-7 Type change of electroactive polymer
  • Example 1-8 Adding a Layer to the Surface of the Polymer Actuator
  • Example 1-9 Change of loading conditions of the electroactive polymer
  • the polymer drive body was prepared by varying the lamination temperature of the electroactive polymer Nafion at 130 C, 200 C and the lamination pressure at 3000 psi and 8000 psi, respectively.
  • Example 1-10 Change in the type of mixed solvent in electroless plating
  • Example i instead of the electroless plating ethanol for forming the electrode layer, the electrode coating under the mixed solvent of water and methanol (100: 20 weight ratio), water and isopropanol (10 (): 20 weight ratio), respectively.
  • the electrode coating under the mixed solvent of water and methanol (100: 20 weight ratio), water and isopropanol (10 (): 20 weight ratio), respectively.
  • Example 1-11 Use of a Single Solvent System in Electroless Plating
  • a polymer driving body was prepared by performing electrode coating under a single solvent of water instead of a mixed solvent of water and ethanol.
  • Example 1-12 Change in the content of the mixed solvent in the electroless plating
  • the polymer was prepared by electrode coating at a composition ratio of 100: 5 weight ratio and 100: 60 weight ratio of water and ethane, respectively. .
  • the electrode coating layer is thinner and thinner than the embodiment 1-1, and the driving performance is lowered.
  • Example 1-13 Recovery change of electroless plating
  • Example 1-1 In the same manner as in Example 1-1, the electroless plating was repeated 2, 3 and 4 times to prepare a polymer driving body.
  • Example 2 In the same manner as in Example 1-1, using a commercially available Nafion membrane without lamination without lamination, the electrode was coated to prepare a catheter.
  • Commercially available Nafion 117 US DuPont
  • Example 1-1 the same procedure as in Example 1-1 was carried out, and the Nafion membrane was manufactured by using three-dimensional constant casting instead of lamination. At this time, the three-dimensional constant casting was made of 15 wt% Nafion solution at a temperature of 60 ° C. while evaporating the solvent within 5 hours at 180 ° (M thickness).
  • a catheter was prepared by adhering the prepared Nafion membrane or a commercially available membrane (Dupont Corporation 175-185 thick Nafion membrane) with Nafion solution ⁇ electrode coating. At this time, the Nafion solution was applied by applying a brush at a concentration of 15% by weight or by applying a Nafion solution with 3 ⁇ 4 coating and then adhesive was prepared by evaporating the solvent within 5 hours at 60 ° C temperature.
  • the ion exchange membrane was manufactured in the same manner as in Example 1-1 except that the Nafion membrane was laminated except for the wire in the lamination process.
  • the following procedure was performed to make the prepared membrane into a polymer driver having bidirectional and tetradirectional properties.
  • the laminated film is cut to a size of 1 mm X 1 ram X 30 mm, and then subjected to the same electrode coating process and insulation process as in Example 1-1.
  • the driving body for the guide wire which can drive in 4 directions was produced.
  • the same electrode coating process as in Example 1-1 was performed without cutting the laminated film.
  • the electrode-coated ionic polymer membrane was cut into a size of 1 mm X 1 mm X 30 mm, and a catheter for guide wires capable of driving in two directions, in which two pairs of electrodes were positioned on two opposite surfaces, was grayed out.
  • each of the guide wire catheter was used by using the polymer driver grayed out in Examples 1-2 to 1-12 and Comparative Examples 1 to 2.
  • the inner ribs made of a conventionally coated stainless steel coil and the outer wall of the inner ribs are covered with a stainless steel coil, and the stainless steel coil and the formed memory alloy coil (TiNiK wire diameter: 30 / m, coil are located in front of the inner tube outer wall). Background: becomes wrapped in the 150 // m) may,. And the whole is covered with a parylene-coated polyurethane, so the active catheter (thickness 1.4 mm)
  • the catheter prepared in Examples 2 and 3 was measured in the physical properties as described below and the results are shown in the following table.
  • Driving force Measure 10 seconds at DC 6V using a laser drive meter.
  • the chord speed means a mechanical response.
  • the electrical response which measures how long it starts to move when an electrical signal is given, occurs in the range of several seconds, making it difficult to measure it in practice.
  • the driving body the hydrated ear is driven by an electrical stimulus from the outside, and the driving speed is increased because the movement speed of ions is less than / s. Based on this, it is based on moving to a range of specific displacement, and it takes how long it takes to reach the point, and sets the mechanical response to the mechanical response speed. Set. With the limit of 15 mm, which is the maximum measurement limit of the current drive displacement accumulator, the time taken to reach the limit was measured, and the reaction rate was measured in units of 'mm / s'.
  • Example 1-1 2.030 33.3 1-5.2 1.43-0.25
  • rod A polymer drive body in which electrodes are coated on four sides of a columnar laminate.
  • tube Polymer driving body in which the duct exists in the longitudinal direction of the lamppost stack and the electrode is coated on the four sides of the lamppost stack.
  • the catheter manufactured using the polymer driving body according to the present invention has a driving force of 0.2 g f or more, a driving displacement of 40 ° or more, a response speed of less than 2.0 mm / s, and an intensity of X 8 is at least 10- 7 Nm 2, it was confirmed that the density of maintaining eu 0.25 g / cm under 3.
  • the catheter manufactured without applying the lamination method (Comparative Example 1) has a very good reaction speed and driving displacement due to the reduction of the rigidity of the ion exchange membrane itself, but due to the significant reduction of the driving force, which is the upper layer of the physical properties.
  • the catheter manufactured by 3D constant casting method (Comparative Example 2) has a problem that it is difficult to insert the metal wire sculpture for forming the internal duct, and therefore, the duct formation is very difficult. It was difficult to make the thickness uniform.
  • the casting to form a catheter sizeable thickness of 900-1100 im thickness occurs simultaneously with the evaporation of the internal solvent and the film formation on the surface during the film formation at high temperature (60-100 ° C) for rapid film production. Cracks on the surface of the membrane
  • the rigidity of the laminated film is increased too much, and when it is formed as a driving body, the displacement is significantly decreased.
  • the catheter using the shape memory alloy (Comparative Example 3) is largely moved based on the volume change using the change of the internal crystal structure of the metal according to the change of silver, which requires smooth and even heat transfer to the inside of the metal. That is, a sufficient drive is made only when a change of the structure is induced in a state in which sufficient heat and time are given.
  • the thermal response rate which requires sufficient time compared to the electrical response rate, is relatively slow (msec ⁇ min). Also
  • the temperature range for driving the shape memory alloy occurs in a higher range than the temperature range for the application in the body, there is a great deal of practical application in the human body.

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Abstract

La présente invention porte sur un actionneur polymère comprenant : (i) un stratifié polymère électroactif en forme de colonne et (ii) une pluralité de couches de revêtement d'électrode présentes sur une partie de la surface du stratifié en forme de colonne, et un cathéter contenant l'actionneur polymère. L'actionneur polymère a une faible densité et des propriétés mécaniques améliorées, telles qu'un déplacement par entraînement, une force d'entraînement et analogue, et une vitesse de réponse, les caractéristiques d'entraînement pouvant être commandées par commande de facteurs, tels que la fonction d'échange d'ions des groupes ioniques présents dans un polymère électroactif, le nombre des groupes ioniques, la distribution des groupes ioniques, le type de contre-cations, l'épaisseur d'une membrane échangeuse d'ions, l'épaisseur d'une électrode de surface et analogue, permettant ainsi au cathéter contenant ledit actionneur polymère d'être facilement utilisé comme fil-guide ou comme cathéter actif.
PCT/KR2010/000534 2010-01-29 2010-01-29 Actionneur polymère, cathéter contenant celui-ci et procédé de préparation de l'actionneur polymère WO2011093542A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114633530A (zh) * 2022-04-07 2022-06-17 合肥工业大学 离子交换膜型多刺激源响应柔性驱动器、制备方法及应用
CN114633530B (zh) * 2022-04-07 2024-06-04 合肥工业大学 离子交换膜型多刺激源响应柔性驱动器、制备方法及应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5954654A (en) * 1997-01-31 1999-09-21 Acuson Corporation Steering mechanism and steering line for a catheter-mounted ultrasonic transducer
US20030055446A1 (en) * 2001-09-20 2003-03-20 Seward Kirk Patrick Microfabricated surgical device for interventional procedures
US20070021685A1 (en) * 2005-05-04 2007-01-25 Abbott Laboratories Abbott Vascular Devices Guidewire apparatus with an expandable portion and methods of use
US7300438B2 (en) * 2001-04-27 2007-11-27 C.R. Bard, Inc. Electrophysiology catheter for mapping and/or ablation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5954654A (en) * 1997-01-31 1999-09-21 Acuson Corporation Steering mechanism and steering line for a catheter-mounted ultrasonic transducer
US7300438B2 (en) * 2001-04-27 2007-11-27 C.R. Bard, Inc. Electrophysiology catheter for mapping and/or ablation
US20030055446A1 (en) * 2001-09-20 2003-03-20 Seward Kirk Patrick Microfabricated surgical device for interventional procedures
US20070021685A1 (en) * 2005-05-04 2007-01-25 Abbott Laboratories Abbott Vascular Devices Guidewire apparatus with an expandable portion and methods of use

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114633530A (zh) * 2022-04-07 2022-06-17 合肥工业大学 离子交换膜型多刺激源响应柔性驱动器、制备方法及应用
CN114633530B (zh) * 2022-04-07 2024-06-04 合肥工业大学 离子交换膜型多刺激源响应柔性驱动器、制备方法及应用

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