JP6043685B2 - Catheter including conductive composite fiber - Google Patents

Description

  The present invention relates to a catheter including a conductive conjugate fiber. More specifically, a conductor including a conductive composite fiber containing a conductive polymer, a lead wire including an insulator including a fluorine-containing polyimide that covers the conductive composite fiber, and an electrode including the conductor. The present invention relates to a conductive composite fiber catheter.

  Due to recent advances in medical technology, a disease treatment method has been replaced by a catheter treatment method in which a medical instrument such as a catheter is directly inserted into a patient's body from a conventional incision operation. A medical lead having an electrode embedded in or in the vicinity of the heart is used to improve arrhythmia or stimulate heart contraction. Furthermore, implantable electrodes are also used for cardiac pacemakers, cochlear implants and the like.

  For example, there is an electrode catheter as a heart disease catheter which is one of the above-described medical devices. As shown in FIG. 7, this electrode catheter 70 includes at least a tip electrode portion 72, a catheter body 74, a plug 74 connecting the extension cable and the catheter, and the like as a basic structure. An electrode 73 is included.

  Since conventional electrical stimulation catheters and medical leads using metal electrodes are hard materials, mechanical stress is large at the point of contact with a flexible living tissue. Such stress can lead to the destruction and scarring of living tissue.

  Furthermore, the various components used in the medical instrument of the type inserted into the body, such as the various components of the catheter and the medical lead, are damaged to the body tissue due to long-term installation in the body, and various components. Depending on the life of the coating applied to the skin, it may be necessary to replace the various components or the medical device itself, particularly when used for a cardiac pacemaker or the like.

  When attention is paid to the material of the electrode used in the medical device as described above, conductive fibers are known as a conductive material that is more flexible than the material of a single metal. As this conductive fiber, there are known those in which a metal such as copper is coated on the surface of the fiber, and those in which carbon or a fine metal wire is woven into the fiber. These conductive fibers are widely used for bioelectrodes, biointerfaces, antistatic clothing and the like. However, since conventional conductive materials such as metal and carbon are hydrophobic and hard, they may have low suitability for use in contact with a body surface or body tissue of a living body that is rich in moisture and flexible.

  In recent years, a conductive polymer that is particularly excellent in conductivity and hydrophilicity has attracted attention as a material having good compatibility with living bodies. For example, the development of conductive fibers using PEDOT-PSS [poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)] has been promoted, and its practical application has been studied (non-patent) Reference 1). The conductive fiber using such a material can be obtained, for example, by forming an aqueous solution of PEDOT-PDSS into a thread shape by extruding it from a nozzle into an acetone coagulation bath.

  Moreover, there exists a polyimide as a material used in a medical field. This polyimide has excellent heat resistance, mechanical strength, chemical stability, etc. In addition, since various products and parts can be produced from the polyimide precursor solution, it has excellent moldability. doing. For this reason, in the medical field, it is used as a material for catheters, endoscopes, tubes for transporting chemicals, and the like.

Spinning and Characterization of Conducting Microfibers ”Macromol. Rapid Commun. (2003) 24, pp261-264

  Conventional catheters and medical tubes use a heparin coat, for example, to prevent blood coagulation, in order to improve compatibility with living tissue. However, since this heparin coat is a protein coating, there are problems in terms of stability, durability, long-term storage and the like. Further, in the above-described medical devices such as catheters and medical tubes, there are many cases where metals, conductive materials, and the like used for the electrodes are not appropriate from the viewpoint of biocompatibility. For example, since conventional electrical stimulation catheters and medical lead wires using metal electrodes are hard materials, there is a problem of poor compatibility with a living body or a problem that blood coagulation easily occurs.

  Moreover, about said conductive fiber, when the conductive fiber which consists of PEDOT-PSS was used in a high humidity environment, PEDOT-PSS absorbed the water | moisture content and there existed a problem which intensity | strength (especially tensile strength) fell. . In addition, the conductive fiber made of PEDOT-PSS expands when it absorbs moisture, and conversely shrinks when dried, so that there is a problem that cracks occur inside the fiber or the fiber breaks. there were. And as a result of such cracks and breaks of the fibers, there has been a problem that the conductivity of the fibers tends to be reduced or lost.

  Furthermore, in the use of bioelectrodes and biointerfaces, the clothing of the subject (patient) with these parts may get wet by rain or sweat when in use, so the usage environment is inherently high in humidity. is there.

  Therefore, in order to utilize PEDOT-PSS excellent in electrical conductivity and hydrophilicity for a wide range of applications envisaged for medical devices, a solution to the above problem in use under high humidity conditions has been demanded. In addition to the above problem that the strength of the conductive fiber made of PEDOT-PSS is significantly reduced when it contains moisture, the fiber is produced by the wet-spinning method described in Non-Patent Document 1. Since the diameter of the fiber is as thin as about 10 microns, the fiber itself is difficult to handle, and there is a problem that the strength is insufficient even during drying.

  In view of the above circumstances, the present invention is to provide a catheter including a conductive composite fiber excellent in biocompatibility, which is excellent in durability, flexible, has little damage to living tissue, and is less likely to cause blood coagulation. Objective.

The present invention relates to a catheter including a conductive conjugate fiber (also referred to herein as a conductive conjugate fiber catheter). The first of this catheter comprises a lead wire and an electrode portion arranged at the end of the lead wire,
The lead wire is
(I) a conductor including a conductive composite fiber containing a conductive polymer; and (ii) an insulator including a fluorine-containing polyimide that covers the conductor;
The electrode unit, viewed contains a conductor of the (i) comprising a conductive composite fibers containing the conductive polymer,
The conductive conjugate fiber is a fiber containing a conductive polymer, the conductive polymer is impregnated and / or attached to a fiber base material, and the conductive polymer is Poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT-PSS),
The fluorine-containing polyimide of the insulating material has a repeating unit represented by the following structural formula (1).

The second of the catheter of the present invention comprises a lead wire and an electrode portion disposed at the end of the lead wire,
The lead wire is
(I) a conductor including a conductive conjugate fiber containing a conductive polymer; and
(Ii) Insulator containing fluorine-containing polyimide covering the conductor
Including
The electrode part includes the conductor (i) including a conductive conjugate fiber containing the conductive polymer,
The conductive composite fiber includes a conductive polymer in a fiber base material, the conductive polymer is impregnated and / or attached to a fiber base material, and the conductive polymer is a polycrystal. (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT-PSS),
The fluorine-containing polyimide of the insulating material has a repeating unit represented by the following structural formula (2).

The third of the catheter of the present invention comprises a lead wire and an electrode portion disposed at the end of the lead wire,
The lead wire is
(I) a conductor including a conductive conjugate fiber containing a conductive polymer; and
(Ii) Insulator containing fluorine-containing polyimide covering the conductor
Including
The electrode part includes the conductor (i) including a conductive conjugate fiber containing the conductive polymer,
The conductive composite fiber includes a conductive polymer in a fiber base material, the conductive polymer is impregnated and / or attached to a fiber base material, and the conductive polymer is a polycrystal. (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT-PSS),
The fluorine-containing polyimide of the insulating material has a repeating unit represented by the following structural formula (3).

4th of the catheter of this invention is equipped with the electrode part arrange | positioned at the lead wire and the edge part of the said lead wire,
The lead wire is
(I) a conductor including a conductive conjugate fiber containing a conductive polymer; and
(Ii) Insulator containing fluorine-containing polyimide covering the conductor
Including
The electrode part includes the conductor (i) including a conductive conjugate fiber containing the conductive polymer,
The conductive composite fiber includes a conductive polymer in a fiber base material, the conductive polymer is impregnated and / or attached to a fiber base material, and the conductive polymer is a polycrystal. (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT-PSS),
The fluorine-containing polyimide of the insulating material has a repeating unit represented by the following structural formula (4).

The fifth of the catheter of the present invention comprises a lead wire and an electrode portion disposed at the end of the lead wire,
The lead wire is
(I) a conductor including a conductive conjugate fiber containing a conductive polymer; and
(Ii) Insulator containing fluorine-containing polyimide covering the conductor
Including
The electrode part includes the conductor (i) including a conductive conjugate fiber containing the conductive polymer,
The conductive composite fiber includes a conductive polymer in a fiber base material, the conductive polymer is impregnated and / or attached to a fiber base material, and the conductive polymer is a polycrystal. (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT-PSS),
The fluorine-containing polyimide of the insulating material has a repeating unit represented by the following structural formula (5).

  Since the conductive composite fiber catheter of the present invention uses a conductive composite fiber containing a conductive polymer as a conductor, it is flexible and has a large electrochemical capacity. In addition, since fluorinated polyimide is used for the insulator, it is flexible (the flexibility can be adjusted) and has excellent heat resistance, stability, durability, and long-term storage. For this reason, it is extremely useful as a catheter for electrical stimulation.

(A) is a schematic diagram which shows an example of the catheter of this invention, (b) is bb sectional drawing of the catheter of (a), (c) is the conductor part of the catheter of (a). It is a schematic diagram which shows, (d) is a schematic diagram which shows an example of the specific structure of an electroconductive composite fiber. (A) is a schematic diagram which shows another example of the catheter of this invention, (b) is bb sectional drawing of the catheter of (a). (A) is a schematic diagram which shows another example of the catheter of this invention, (b) is bb sectional drawing of the catheter of (a), (c) is c- of the catheter of (a). It is c sectional drawing. (A) is a schematic diagram which shows another example of the catheter of this invention, (b) is bb sectional drawing of the catheter of (a). It is a schematic diagram which shows another example of the electroconductive composite fiber catheter of this invention. It is a schematic diagram which shows another example of the electroconductive composite fiber catheter of this invention. It is the schematic which shows the general structure of the conventional electrode catheter.

  The conductive composite fiber catheter of the present invention comprises at least a lead wire and an electrode portion disposed at one end of the lead wire. Other components may include, for example, an electrode catheter, a plug, an actuator for operating the distal end portion of the catheter, and the like.

  Hereinafter, the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the specific embodiments illustrated in the drawings, and may be appropriately changed or modified within the principle and scope of the specific embodiments. Those skilled in the art will appreciate that the modified invention is also within the scope of the present invention.

  As an embodiment, the conductive composite fiber catheter 100 shown in FIG. 1 can be exemplified. 1A is a schematic view showing an end portion of the conductive composite fiber catheter on the side where electrodes are installed, and FIG. 1B is a cross-sectional view taken along line bb in FIG. 1A. It is.

  As shown in FIG. 1 (a), this catheter includes a lead wire (catheter body portion) 102 and an electrode portion 104. The lead wire 102 includes (i) a conductive composite fiber containing a conductive polymer. And (ii) an insulator 110 containing a fluorine-containing polyimide (also referred to herein as fluorinated polyimide) covering the conductor (ii). As shown in FIG. 1B, the conductor 106 of the lead wire 102 is preferably covered with an insulator 110. In the present invention, the conductor is only required to be covered with an insulator, and the shapes of the conductor and the insulator are not limited to the cylindrical core-sheath structure as shown in FIG. For example, the conductor may have a cross section other than a circle such as an ellipse or a rectangle, and the insulator may similarly have a cross section whose shape is an ellipse or a rectangle.

  It is preferable that the electrode part 104 contains the conductive composite fiber similar to the conductor (a). The electrode portion 104 may be separately connected to the tip end portion of the conductor 106 of the lead wire 102 and may be provided with the same material as or a different material from the conductor 106, and the conductor 106 extends from the tip end portion of the lead wire 102. What is exposed by doing (for example, FIG.1 (c)) may be sufficient. In the present invention, as in the latter case, it is preferable from the standpoint of manufacturing that the conductor 106 is exposed by extending from the tip of the lead wire 102.

  Although all the electrode parts 104 shown by Fig.1 (a) are the exposed forms, this invention is not limited to this. For example, the electrode part 104 may have a shape in which a part thereof is covered with an insulating material, or a shape in which the conductive composite fiber of the electrode part is exposed at a plurality of sites.

  The conductor 106 and the electrode part 104 include a conductive composite fiber. For example, the conductive conjugate fiber includes a fiber base 114 and a conductive polymer 116 as indicated by reference numeral 112 in FIG. In the form shown in FIG. 1 (d), the structure in which the periphery of the fiber base material 114 is covered with the conductive polymer 116 is shown as one embodiment. However, the present invention is not limited to this, and the fiber base material 114 may be impregnated with the conductive polymer 116.

  As shown in FIG. 1 (d), when the conductive polymer 116 is coated around the fiber base 114 as a core, the conductive conjugate fiber 112 has a large adhesion area at the boundary between them. Thus, the conductive composite fibers can be sufficiently bonded to each other. In such a structure, the conductor is reinforced by the fiber base material 114 rather than the conductor 106 formed of a single conductive polymer. Therefore, compared with the conductor using the fiber comprised only from the conductive polymer, the conductor 106 of this embodiment can increase the strength. Further, the flexibility of the fiber base material 114 used as the core is imparted to the conductive conjugate fiber 112. The same applies to the conductor using the conductive conjugate fiber 112 in which the fiber base material 114 is impregnated with the conductive polymer 116.

  As described above, the conductive conjugate fiber can have a structure in which a conductive polymer is coated around the fiber base material. In this case, the thickness h (see FIG. 1D) of the conductive polymer coated around the fiber substrate is not particularly limited. For example, the thickness can be 0.001 to 2 times the diameter L of the fiber substrate. More specifically, when the fiber base material is, for example, 2 to 3 denier (D) silky silk fiber, that is, silk fiber having a fiber base diameter of about 10 to 15 microns, h is 0. .01 microns to 10 microns may be used.

  By covering the periphery of the fiber base material with the conductive polymer, the conductivity of the conductive conjugate fiber is further increased, and it is easier to bring the plurality of conductive conjugate fibers into contact with each other for conduction. In addition, when the thickness is within the above range, the conductive conjugate fiber has better conductivity without impairing its flexibility. In the said range, it becomes a fiber which has higher electrical conductivity, so that the thickness h of a conductive polymer is thick. Therefore, by adjusting the thickness h of the conductive polymer, the conductivity or electrical resistance of the conductive composite fiber can be adjusted.

  Even when the fiber base material is impregnated with the conductive polymer, the same effect as in the case of the coating can be obtained. In the case of impregnation, since the conductive polymer enters from the surface of the fiber base toward the inside, a concentration gradient of the conductive polymer occurs inside the fiber base. Accordingly, even by such impregnation, the conductivity or electrical resistance of the conductive composite fiber can be adjusted by adjusting the impregnation time.

  In addition, although the conductive conjugate fiber described above can be suitably used for the conductive conjugate fiber catheter of the present invention, in addition to this application, it can be used for clothing, medical instruments other than catheters, bioelectrodes, biointerfaces, and the like. Can be used.

  Next, a method for forming a conductive conjugate fiber will be described. Examples of the method for forming the conductive conjugate fiber include the following methods. By applying a coating solution containing a conductive polymer and a diluting solvent onto the fiber substrate [for example, dipping (dip coating), spraying (spray coating), etc.] and drying the solvent, the fiber substrate and the conductive polymer are dried. A conductive conjugate fiber containing may be formed. As will be described later, the coating solution may contain an additive in addition to the conductive polymer. The fiber substrate may be a single fiber or a bundle of a plurality of fibers.

  As another method for producing a conductive composite fiber as a fiber bundle, a method of forming a conductive composite fiber as a single fiber as described above, and combining a plurality of these can be exemplified.

  Examples of the method of applying or impregnating include a method of preparing a solution containing a conductive polymer and an additive as necessary, and immersing (dip coating) a fiber substrate in the solution.

  The conductor 106 of the lead wire and the conductor 108 of the electrode part can be formed using the above-described conductive composite fiber, for example, as follows. When the conductor 108 in the electrode portion is exposed by extending the conductor 106 from the distal end portion of the lead wire 102, the conductor 106 and the conductor 108 in the electrode portion 104 are integrated with the conductive composite fiber. What is necessary is just to form. Further, when the conductor 108 of the electrode portion 104 is separately connected to the tip end portion of the conductor 106 of the lead wire 102, the electrode portion and the conductor of the lead wire are respectively formed from conductive composite fibers, and the fibers of the connection portion are formed. The conductor 108 of the electrode portion is formed at the tip of the conductor 106 of the lead wire by twisting or joining the connecting portions so as to be electrically conducted by appropriate means such as screwing and fitting. can do.

  The conductor 106 of the lead wire and the conductor 108 of the electrode portion may be configured to include any material in addition to the conductive composite fiber. For example, reinforcing fibers other than conductive composite fibers may be woven. In the present invention, it is preferable to form the conductive composite fiber alone.

  The method for producing a conductive conjugate fiber catheter of the present invention includes covering the periphery of the conductive conjugate fiber with an insulator, preferably a fluorinated polyimide. As an embodiment of a specific coating method, a precursor solution of fluorinated polyimide [for example, polyamic acid solution or polyimide coating agent] or a fluorinated polyimide solution [for example, chemical imidization (for example, dehydration condensation) A polyimide solution prepared by a chemical reaction using an agent and an imidization catalyst), and immersing the conductive composite fiber that becomes the core wire of the lead wire in the precursor solution of the fluorinated polyimide (dip) Coating). Alternatively, a method of spraying a precursor solution of fluorinated polyimide onto the core wire (spray coating) can also be applied.

  In the above-described embodiment in which the conductor of the electrode portion is formed integrally with the conductor of the lead wire, the tip of the conductive composite fiber may be exposed. What is necessary is just to immerse the site | parts of electroconductive composite fibers other than a part in the precursor solution of insulator material, or the solution of insulator material. In the case of the spraying method, the tip part (the part corresponding to the electrode part) to which the conductive composite fiber is exposed is previously protected with a protective cap, tape, etc., and the precursor solution of the insulator material is applied to the entire conductive composite fiber Alternatively, a protective cap, a tape, or the like may be removed after spraying a solution of an insulating material and spraying. After coating, when a fluorinated polyimide precursor solution is used, imidization may be performed by heating the coated conductive conjugate fiber in an oven at a temperature of 300 to 400 ° C. Moreover, when using a fluorinated polyimide solution, what is necessary is just to heat-dry at the temperature (for example, 55-170 degreeC) which can remove the solvent after the coating for the coated conductive conjugate fiber. In addition, also in the case of the electrode part which has the shape which the conductive composite fiber of the electrode part exposed in the several site | part, it can obtain by the method similar to the above. That is, it is only necessary to protect only the portion of the electrode portion that is desired to be exposed with a protective cap and tape. By such means, a conductive composite fiber catheter is obtained in which the conductive composite fiber of the lead wire is covered with an insulating material of fluorinated polyimide and the conductive composite fiber of the electrode portion at the distal end portion of the catheter is exposed.

  The flexibility of the conductive composite fiber catheter of the present invention can be adjusted by the type and thickness of the fiber substrate used, the type of fluorinated polyimide film, the type of molded product or laminate, the thickness, and the molding temperature. Furthermore, the electrode part of the catheter exposes a conductor containing conductive composite fibers, and this exposed part can serve as an in vivo electrode.

  Next, a second embodiment of the conductive composite fiber catheter of the present invention will be described. The catheter of this embodiment has a structure shown in FIG. 2, for example. Here, Fig.2 (a) is a schematic diagram which shows the front-end | tip part by the side of the electrode part of the lead wire of the catheter 20 of 2nd embodiment, and an electrode part. FIG. 2B is a cross-sectional view taken along line bb of FIG.

  In the present embodiment, as shown in FIGS. 2A and 2B, the lead wire described with reference to FIG. 1 includes the first base portion 21 and the first base portion provided on the first base portion. It has an insulator composed of two base parts 23, and has a structure in which conductive composite fibers 22 are embedded between the first base part 21 and the second base part 23. In the present embodiment, the first base portion 21 and the second base portion 22 of the insulator have a structure (for example, a needle shape) that narrows toward the distal end portion of the catheter. In the present embodiment, the first base and the second base can be fluorinated polyimide films (for example, a film thickness of 20 to 200 μm). In this way, tissue damage can be minimized when the catheter is inserted into a human body or the like. In the present invention, the first base 21 and the second base may have a shape other than the film. Further, the tip shapes of the first base and the second base are not limited to the shapes shown in FIG. 1A, and any shape can be used as long as tissue damage can be minimized. It may be a simple shape.

  In the present embodiment, the second base portion 23 has a structure shorter than the first base portion 21, whereby the conductive conjugate fiber 24 is exposed at the position of the electrode portion 104 of the catheter. . Therefore, in this embodiment, the 1st base 21 supports the electroconductive composite fiber of the electrode part 104 from one side. For this reason, the strength of the conductive conjugate fiber of the electrode part can be further increased by using the first base part as a support. In this embodiment, as shown in FIG. 2B, the cross section of the insulator has a rectangular shape. However, the present invention is not limited to this, as described with reference to FIG. This is the same as the embodiment.

  The manufacturing method of the electroconductive composite fiber catheter of this embodiment is demonstrated below. First, portions corresponding to the first base portion 21 and the second base portion 22 are manufactured as a fluorinated polyimide film, molded product, or laminate. Next, the conductive conjugate fiber is disposed on the obtained first base portion 21. Further, the second base portion 22 is installed so as to expose the electrode portion of the conductive conjugate fiber and cover the other portion, and the first and second base portions and the conductive conjugate fiber are crimped and thermocompression bonded. And may be joined by means such as adhesion. More specifically, first, the conductive conjugate fiber 23 is disposed on a thin strip-like fluorinated polyimide film 21 (first base portion) whose tip portion has been thinned. Further, a strip-like fluorinated polyimide film 22 (second base) having a thin tip is exposed on the side where the conductive composite fiber of the first base 21 is disposed, and the conductor 24 of the electrode portion is exposed. And the whole may be joined by pressure bonding or the like. Thereby, the electroconductive composite fiber catheter which the electroconductive composite fiber exposed in the front-end | tip part of a catheter can be obtained.

  The flexibility of the conductive composite fiber catheter of the present invention can be adjusted by the type and thickness of the fiber substrate used, the type of fluorinated polyimide film, the type of molded product or laminate, the thickness, and the molding temperature. Furthermore, a conductor including a conductive composite fiber is partially exposed in the electrode portion, and this exposed portion can be an in vivo electrode.

  Next, a third embodiment of the conductive composite fiber catheter of the present invention will be described with reference to FIG. FIG. 3A is a schematic diagram showing the distal end portion on the electrode portion side of the lead wire of the catheter 30 of the third embodiment and the electrode portion. FIG. 3B is a cross-sectional view taken along line bb of the electrode portion in FIG. FIG. 3A is a cross-sectional view taken along the line cc of the lead wire.

  In the present embodiment, as shown in FIGS. 3A to 3C, the lead wire described with reference to FIG. 1 includes the first base portion 21 and the first base portion provided on the first base portion. It has an insulator composed of two base portions 33 and has a structure in which the conductive conjugate fiber 22 is embedded between the first base portion 21 and the second base portion 33. The insulator composed of the first base portion 21 and the second base portion 33 has a structure (for example, a needle shape) that becomes narrower toward the distal end portion of the catheter. Therefore, in this embodiment, the electrode portion 104 is covered with an insulator extending from the lead wire, and this insulator is directed toward the tip of the catheter on the side where the electrode portion is present, as shown in FIG. It has a structure that narrows. In this way, tissue damage can be minimized when the catheter is inserted into a human body or the like. In the present invention, the shape of the distal end of the first base portion 21 and the second base portion 33 as shown in FIG. 3A is not limited, and a shape that can minimize tissue damage. Any shape can be used.

  In the present embodiment, since the electrode portion 104 is covered with the first base portion 21 and the second base portion 33, as shown in FIG. 3B, the electrode portion 104 has at least the second conductive conjugate fiber 22. The base 33 has an opening 34 communicating with the outside. As a result, the conductive conjugate fiber 24 is exposed at a part of the electrode portion of the catheter. 3A and 3B, the opening 34 is formed in the second base 33 of the electrode part. However, the present invention is not limited to this, and the first base 21 of the electrode part 104 is formed. Can be formed, or can be formed on both the first base and the second base 33. Moreover, in this embodiment, as shown in FIG. 3B, the cross section of the insulator has a rectangular shape. However, the present invention is not limited to this, and the first embodiment described with reference to FIG. It is the same as the form.

  The manufacturing method of the electroconductive composite fiber catheter of this embodiment is demonstrated below. First, portions corresponding to the first base portion 21 and the second base portion 33 are manufactured as a fluorinated polyimide film, molded product, or laminate. Next, the conductive conjugate fiber is disposed on the obtained first base portion 21. Further, a fluorinated polyimide film, molded product or laminate corresponding to the second base 33 having the opening 34 is installed so as to cover the conductive conjugate fiber, and the first and second bases, and the conductive What is necessary is just to join a composite fiber by means, such as pressure bonding, thermocompression bonding, and adhesion. More specifically, the conductive composite fiber is first disposed on a thin strip-like fluorinated polyimide film 21 (first base) that is thinly processed toward the tip. Next, a thin strip-like fluorinated polyimide film 33 (second base) provided with an opening 34 is disposed on the side of the first base 21 where the conductive conjugate fiber is disposed, What is necessary is just to join by crimping etc. Thereby, the conductive conjugate fiber catheter of the present embodiment has a structure in which the conductive conjugate fiber is exposed at the opening at the distal end portion of the catheter. Note that the opening of the second base is formed by a punching means such as punching when the second base is a film, an appropriate mold is used for a molded product, and punching, etching, etc. is used for a laminate. Can be provided by any suitable means.

  The flexibility of the conductive composite fiber catheter of the present invention can be adjusted by the type and thickness of the fiber substrate used, the type, thickness, and molding temperature of the fluorinated polyimide film or molded product or laminate. Furthermore, a conductor including a conductive composite fiber is partially exposed in the electrode portion, and this exposed portion can be an in vivo electrode.

  Next, as a fourth embodiment of the present invention, a conductive conjugate fiber catheter (the conductive conjugate fiber is rectangular) shown in FIG. 4 can be exemplified. Fig.4 (a) is a schematic diagram which shows the front-end | tip part by the side of the electrode part of the lead wire of the catheter 40 of 4th embodiment, and an electrode part. FIG. 4B is a cross-sectional view taken along the line bb of the electrode portion in FIG.

  This embodiment is the same as the second embodiment except that the conductive conjugate fiber is rectangular in the second embodiment. For example, when the conductive conjugate fiber is a single fiber, the conductive conjugate fiber including the conductive polymer may be formed in a rectangular shape. Alternatively, when the conductive conjugate fiber is a fiber bundle, a method of bundling a plurality of single fibers of the conductive conjugate fiber containing a conductive polymer and compressing it into a rectangular shape can be exemplified.

  In the present embodiment, as in the second embodiment, since the first base 21 has a structure that supports the conductor, the conductor is made of only a conductive polymer that does not use a fiber base material. You can also A catheter including such a conductor, for example, creates a first base 21 and a second base 42 from a film, molded article or laminate of a fluorinated polyimide, and then conductive on the first base 21. It is obtained by applying a coating solution containing a conductive polymer and heating and drying to form the conductor 42 in the lead wire portion and the conductor 44 in the electrode portion 104. As a coating method, a general screen printing, pattern printing, spray coating method or the like can be used using a coating solution such as an emulsion solution of PEDOT-PSS. As another coating method, a method of forming a conductor in a pattern by discharging (discharging) a solution containing PEDOT-PSS from a nozzle or the like can be used. Next, the second base 42 is disposed on the side where the conductor of the first base 21 is laid, and is processed in the same manner as in the second embodiment to form a catheter.

  The flexibility of the conductive composite fiber catheter of the present invention can be adjusted by the type and thickness of the fiber substrate used, the type of fluorinated polyimide film, the type of molded product or laminate, the thickness, and the molding temperature. Furthermore, a conductor including a conductive composite fiber is partially exposed in the electrode portion, and this exposed portion can be an in vivo electrode.

  Next, in the fifth embodiment of the present invention, the structure of the conductor of the electrode portion of the conductive composite fiber catheter is a loop shape, a snare shape, a club shape, or the like. This embodiment is a modified example in which the structure of the conductor of the electrode portion 104 of the conductive composite fiber catheter 100 of the first embodiment described above is modified.

  FIG. 5 shows that the structure of the conductor 52 of the electrode portion 104 in the present embodiment is a loop (loop electrode). Specifically, the conductive composite fiber catheter of this embodiment includes a lead wire (catheter body portion) 102 and an electrode portion 104. Among these, the configuration of the lead wire 102 is as described in the first embodiment. In the electrode portion 104, the tip portion 52 of the conductive conjugate fiber (conductor) exposed from the end portion of the lead wire 102 has a ring shape.

  As another modification of the present embodiment, FIG. 6 shows a structure in which the conductor 62 of the electrode portion 104 has a rod-like shape (rod-like electrode). Specifically, the conductive composite fiber catheter of the present embodiment includes a lead wire (catheter main body portion) 102 and an electrode portion 104. Among these, the configuration of the lead wire 102 is the same as that of the first embodiment. As explained. Further, in the electrode portion 104, the tip portion 62 of the conductive conjugate fiber (conductor) exposed from the end portion of the lead wire 102 has a club-like shape. As another modification, although not shown, the structure of the conductor 62 of the electrode portion 104 can be a snare (snare electrode).

  These conductive composite fiber catheters can be manufactured, for example, by the following method. For example, in the case of the loop-shaped electrode shown in FIG. 5, the end portion 52 of the conductive composite fiber (conductor) exposed from the end of the lead wire 102 is folded back, and the fiber is placed near the end of the lead wire 102. A press machine in which the periphery of the contact portion is protected with, for example, a small piece of a film of fluorinated polyimide after twisting or contacting the base and tip of the conductive composite fiber exposed near the end of the lead wire 102 It is possible to make it into a loop by sticking together with pressure bonding. Alternatively, an electrical composite fiber (conductor) whose tip is processed in a loop shape, a snare shape, or a bar shape in advance is attached, for example, by sandwiching it with a fluorinated polyimide film leaving the loop portion and crimping with a press machine. By combining them, an electrode shape as shown in FIG. 5 or 6 can be obtained. Needless to say, the shape of these electrode tips 52 is not limited to the shape shown in FIG. 5 or 6, and the manufacturing method is not limited to the above-described method.

  The flexibility of the conductive composite fiber catheter of the present invention can be adjusted by the type and thickness of the fiber substrate used, the type of fluorinated polyimide film, the type of molded product or laminate, the thickness, and the molding temperature. Furthermore, a conductor including a conductive composite fiber is partially exposed in the electrode portion, and this exposed portion can be an in vivo electrode.

  Below, the various materials which can be used for the said component of the electroconductive composite fiber catheter of this invention are demonstrated.

(I) Conductive conjugate fiber The conductive conjugate fiber includes a fiber base material and a conductive polymer as described above.

(I-1) Fiber substrate The fiber substrate that can be used in the present invention is not particularly limited as long as it is made of a polymer. For example, synthetic fiber, vegetable fiber, animal fiber, or the like can be used.

  Examples of synthetic fibers include nylon, polyester, acrylic, aramid, polyurethane, and carbon fiber. Examples of plant fibers include cotton, hemp, jute and the like. Examples of animal fibers include silk, wool, collagen, and elastic fibers constituting animal tissues.

  Among these exemplified fiber base materials, animal fibers (proteins) having excellent adhesion to conductive polymers, high strength in dry and wet states, and flexibility suitable for uses such as clothing. Containing fiber) is preferred. In particular, a conductive polymer, which will be described later, and silk fibers excellent in adhesion to PEDOT-PSS and hydrophilicity are more preferable.

  Examples of silk fibers that can be used as the fiber substrate include natural silk fibers of spiders, spiders, and bees, and artificial silk fibers using genetic recombination techniques. Silk, which contains a protein called fibroin, is a fiber that has excellent hydrophilicity, biocompatibility, and dyeability, as used in clothing and surgical threads. One of the fibers. Therefore, it can be suitably used as the fiber base material of the present invention.

  The silk fiber that can be preferably used in the present invention may be either an unprocessed raw silk from which sericin, a glue component, has not been removed, or a kneaded yarn from which part or all of sericin has been removed. From the viewpoint of increasing the adhesion to the conductive polymer and the strength of the conductive composite fiber, a kneaded yarn is more preferable.

  The fiber substrate may be a hollow fiber or a solid fiber. The hollow fiber is suitable for transporting a chemical solution in a catheter as described later. In particular, it is effective when the fiber base is only one fiber. Moreover, even if it is a solid fiber, a chemical | medical solution can be similarly transported by using a fiber bundle.

  The diameter (thickness) of the fiber base material is not particularly limited, and may be appropriately selected depending on the application. When used for clothing, bioelectrodes, and biointerfaces, for example, a diameter of 1 μm to 100 μm is preferable.

  The length of the fiber base material is not particularly limited, and may be appropriately selected depending on the application. For example, the electrode for implantation into a catheter or living tissue of the present invention is 10 μm to 10 cm, 1 mm to 50 cm when used for a biointerface on the body surface, and 1 cm to 100 m as a fiber material for weaving or weaving into clothing. I just need it.

  The fiber base material may be a material obtained by twisting a plurality of fiber base materials into a twisted yarn having a desired thickness, or a mixed spun yarn obtained by mixing different types of fiber base materials. For the purpose of improving the hydrophilicity of the fiber substrate, the fiber substrate may be subjected to various treatments such as plasma treatment, pore treatment, and chemical coating.

(I-2) Conductive polymer The conductive conjugate fiber includes a conductive polymer (conductive polymer). The conductive conjugate fiber can be composed only of the fiber base and the conductive polymer. Alternatively, the conductive conjugate fiber may contain other additives in addition to the fiber base and the conductive polymer.

  PEDOT-PSS, which is excellent in conductivity and hydrophilicity, is suitable for the conductive polymer used in the conductive conjugate fiber. PEDOT-PSS is a conductive polymer obtained by polymerizing 3,4-ethylenedioxythiophene, which is a monomer, in the presence of poly (4-styrenesulfonic acid). PSS functions as a dopant that imparts a negative charge to PEDOT. From the viewpoint of increasing the conductivity of the conductive conjugate fiber that can be used in the present invention, the conductive polymer preferably contains a dopant.

  The inventors of the present invention have found that the adhesion between PEDOT-PSS and a fiber containing a protein such as silk is particularly excellent, and the adhesive surfaces of both are not easily peeled off. Based on this knowledge, in the present invention, it is preferable to use silk fiber as the fiber base material and PEDOT-PSS as the conductive polymer contained in the conductive composite fiber.

  In addition to PEDOT-PSS, examples of the conductive polymer that can be used in the present invention include polyaniline sulfonic acid and polypyrrole. The conductive polymer contained in the conductive conjugate fiber may be one type or a combination of two or more types.

  The molecular weight of the conductive polymer used in the present invention is not particularly limited, and for example, those in the range of several thousand to several hundred thousand can be used.

(I-3) Additive The conductive conjugate fiber may contain an additive other than the conductive polymer. Examples of such additives include glycerol, sorbitol, polyethylene glycol-polypropylene glycol copolymer, ethylene glycol, sphingosine, phosphatidylcholine, and the like. One type of additive contained in the conductor may be used, or two or more types may be combined.

  The above-mentioned additive is used as a bioelectrode for the purpose of adjusting the wetting property of a conductive composite fiber containing a conductive polymer such as PEDOT-PSS or by imparting flexibility to the conductive composite fiber. In particular, it can be used for the purpose of improving the affinity with a living tissue (skin or tissue).

  Specific examples of the adjustment of the wetting property include, for example, adjustment of water absorption of the conductive conjugate fiber, adjustment of wetness or drying of the conductive conjugate fiber (which can prevent excessive expansion or contraction), and the like. Can be mentioned.

  In the present invention, it is preferable to use a combination of PEDOT-PSS and the additive because it is possible to prevent particularly excessive expansion and contraction by adjusting the wetting characteristics of the conductive composite fiber. The reason for this is considered that PEDOT-PSS having high water absorption contains an additive in advance, so that there is less room for moisture to enter later. Among the above-mentioned additives, glycerol, sorbitol, and polyethylene glycol-polypropylene glycol copolymer are particularly preferred as additives used for the purpose of adjusting the wetting characteristics of PEDOT-PSS and further imparting flexibility.

  The conductive composite fiber containing the additive and PEDOT-PSS is preferable because it does not cause excessive water absorption even when used in a high humidity environment, has high fiber strength, and is excellent in conductivity. Moreover, since such a conductive conjugate fiber also has excellent flexibility, the stiff feeling (rigidity) of PEDOT-PSS is alleviated, and has excellent contact properties and affinity with living tissue. Therefore, the conductive composite fiber having a conductor containing an additive and PEDOT-PSS can be a bioelectrode capable of measuring a biosignal with little noise.

  The additive contained in the conductive conjugate fiber is not limited to the above example, and for example, a known organic solvent such as a surfactant, alcohol, natural polysaccharide, sugar alcohol, dimethyl sulfoxide, or the like can be used.

  Examples of the surfactant include known cationic surfactants, anionic surfactants, nonionic surfactants, and the like. These surfactants may be used alone or in combination of two or more.

  Examples of the cationic surfactant include quaternary alkyl ammonium salts and alkylpyridinium halides. Examples of the anionic surfactant include alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, and fatty acid salts. Examples of the nonionic surfactant include polyoxyethylene and polyoxyethylene alkyl ether.

  Examples of the alcohol include known monohydric alcohols and polyhydric alcohols. These alcohols may be used alone or in combination of two or more.

  Examples of the monohydric alcohol include methanol, ethanol, propyl alcohol, isopropyl alcohol, and butanol. The carbon skeleton constituting these alcohols may be linear, branched or cyclic.

  Examples of the polyhydric alcohol include glycols such as ethylene glycol, chain polyhydric alcohols such as glycerin, cyclic polyhydric alcohols such as glucose and sucrose, polymer forms such as polyethylene glycol, polyvinyl alcohol, and polyethylene glycol-polypropylene glycol copolymers. A polyhydric alcohol etc. are mentioned.

  Examples of natural polysaccharides include chitosan, chitin, glucose, and aminoglycan.

  Examples of the sugar alcohol include sorbitol, xylitol, erythritol and the like.

(I-4) Insulator The lead wire of the catheter of the present invention includes an insulator. The insulator material is preferably fluorinated polyimide. Since polyimide has an imide ring in the molecule, it has high heat resistance, and since the polarity of the carbonyl group (C = 0) constituting the imide ring is high, it has a feature of high hydrophilicity. The fluorinated polyimide in which fluorine is introduced into at least a part of carbon atoms of the polyimide hardly causes blood coagulation and has excellent biocompatibility. In the present invention, it is possible to use fluorinated polyimide as the insulating material for the lead wire, but if the fluorine content in the repeating unit constituting the polyimide is small, the biocompatibility effect tends to be small. On the contrary, when the fluorine content in the repeating unit constituting the polyimide increases, the heat resistance and molding processability tend to be lowered. For this reason, it is preferable that the fluorinated polyimide which can be utilized by this invention is a fluorinated polyimide which has a repeating unit represented by either of following Structural formula (1)-(5).

  In the present invention, the conductive conjugate fiber as described above is a hollow single fiber containing a conductive polymer or a fiber bundle of fibers containing a conductive polymer, so that the drug is transported through the conductive conjugate fiber. It is possible. Specifically, a hollow single fiber containing a conductive polymer or a fiber bundle of fibers containing a conductive polymer is impregnated with a drug, and the single fiber or fiber bundle is inserted into a living body, and an electric current is applied, for example. By applying, the drug can be administered (delivered) to a desired site. Alternatively, it is possible to deliver a drug to a desired site by utilizing the capillary action of a hollow single fiber containing a conductive polymer or a fiber bundle of fibers containing a conductive polymer. In addition, the catheter of the present invention can be electrically stimulated by applying an electric current, or can be used as an electrode catheter for physiological examination by detecting a biological signal.

  Even when the conductive composite fiber catheter of the present invention is used for transporting such a drug, the conductive polymer is preferably PEDOT-PSS and the insulator is preferably fluorinated polyimide. Moreover, the above-mentioned additives can be appropriately contained in the conductive conjugate fiber.

  Agents that can be transported with conductive conjugate fibers include anti-infective agents such as antibiotics and antiviral agents; analgesics or anesthetics including fentanyl, sufentanil, buprenorphine, or combinations thereof; anorexics; Anti-arthritic drugs; anti-asthmatic drugs such as terbutaline; anticonvulsants; antidepressants; antidiabetic drugs; antidiarrheal drugs; antihistamines; anti-inflammatory drugs; migraine preparations; Antiemetics; Antitumor drugs; Antiparkinsonian drugs; Cardiotimulants such as dobutamine; Anti-itch drugs; Antipsychotic drugs; Antipyretic drugs; Antispasmodic drugs such as gastrointestinal and bladder; Sympathomimetic drugs; xanthine derivatives; cardiovascular drugs including calcium channel blockers such as nifedipine; beta blockers, salbutamol or litho; Β-agonists such as phosphorus; antiarrhythmic drugs; antihypertensive drugs such as atenolol; ACE inhibitors; diuretics; global, vasodilators including coronary, peripheral, or brain; central stimulants; cold drugs; Relief Agent; Diagnostic Agent; Parathyroid Hormone; Hormone such as Growth Hormone or Insulin; Hypnotic, Immunosuppressant; Muscle Relaxant; Parasympathetic Blocker; Parasympathetic Agent; Antioxidant; Psychostimulants; sedatives; therapeutics in all major therapeutic areas including tranquilizers; carotenoids; ascorbic acid (vitamin C), antioxidants that work on the skin, such as vitamin E, and these act on the skin Vitamin preparations and antioxidants; anti-wrinkle agents such as retinoids including retinol (vitamin A alcohol); α-hydroxy acids; salicyl Β-hydroxy acids such as; combinations of hydroxy acids and polyhydroxy acids; hydrolyzed and soluble collagen, hyaluronic acid or humectants such as these; retinoic acid, hydroquinone or peroxide, and skin bleaching agents such as these; Plant preparations such as aloe vera, wild yam, witch hazel, yam carrot, green tea, and medicinal plant extracts are included.

  Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to such examples.

(Production of conductive composite fiber catheter)
Example 1
A silk fiber bundle (made by Fujix Co., Ltd., tire No. 9, fiber diameter of about 280 μm) before being converted into a composite fiber is 0. It was immersed in a 1% added solution. Subsequently, the silk fiber bundle is energized using a comb-shaped electrode, and the PEDOT-PSS is electrochemically fixed on the surface and inside of the silk fiber bundle to obtain a fiber bundle of the silk fiber bundle and the PEDOT-PSS. It was. Next, the obtained fiber bundle was impregnated with glycerol. Furthermore, once again, immersion in a solution in which 0.1% of EDOT (manufactured by Heraeus Germany) was added to PEDOT-PSS (Clevios P, manufactured by Heraeus Germany), electrolysis, and impregnation with glycerol were performed electrochemically. By fixing PEDOT-PSS, a conductive composite fiber bundle containing a silk fiber bundle, PEDOT-PSS and glycerol was obtained.

  Next, the following structural formula (1):

A precursor solution of fluorinated polyimide represented by the formula (N, N-dimethylacetamide solution of polyamic acid) is spin-coated on a silicon substrate by spin coating so that the final film thickness is 50 μm, and this is applied to nitrogen. Heating was performed at 350 ° C. for 1 hour in an oven under a gas atmosphere. Thereafter, it was allowed to cool, and after the temperature dropped to near room temperature, the silicon substrate was taken out and the fluorinated polyimide film was peeled off from the silicon substrate. The obtained fluorinated polyimide film has a strip shape having a length of 50 mm, a width of 3 mm, and a thickness of 50 μm as shown in the first base of FIG. 2 (a), with one end portion directed toward the tip portion. It cut out so that it might become a thin needle shape, and obtained the 1st base. A conductive composite fiber bundle containing the silk fiber bundle, PEDOT-PSS, and glycerol was placed at the center in the width direction of the fluorinated polyimide film. Next, the 2nd base of the fluorinated polyimide film produced by the method similar to the 1st base of the above-mentioned fluorinated polyimide film was produced except changing heating temperature at 250 ° C for 1 hour. As shown in the second base of FIG. 2 (a), the obtained film has a strip shape with a length of 40 mm, a width of 3 mm, and a thickness of 50 μm, and is directed toward both ends of the second base. Was cut out in a needle shape. This was placed on the conductive composite fiber bundle of the first base part placed on the fluorinated polyimide so that both ends of the fiber bundle were exposed by 5 mm each. This was pressure-bonded with a press machine to produce a conductive composite fiber catheter. As a result of calculating the resistance value of this catheter from the amount of current at the time of DC5V load using a DC stabilized power supply (PAB18-5.5; manufactured by Kikusui Electronics Co., Ltd.) and a digital multimeter (VOAC7511; manufactured by Iwasaki Tsushinki Co., Ltd.) The resistance value was 0.02 MΩ / cm, and the conductivity was 0.1 S / cm.

(Example 2)
By the same operation as in Example 1, a conductive composite fiber bundle containing a silk fiber bundle, PEDOT-PSS and glycerol was obtained. Each 5 mm at both ends of the fiber bundle was protected with polyimide tape.

  Next, the following structural formula (2) prepared by chemical imidization

The conductive composite fiber bundle obtained previously was immersed in an acetone solution of a fluorinated polyimide having a repeating unit represented by the following, and then dried in an oven at 80 ° C. This dipping and drying operations were repeated three times, and finally, the polyimide tape that protected the tip of the conductive composite fiber bundle was removed to produce a conductive composite fiber catheter.

  As a result of measuring the resistance value and the conductivity in the same manner as in Example 1, they were 0.02 MΩ / cm and 0.1 S / cm, respectively.

Example 3
A conductive composite fiber catheter (length: 20 mm, conductive composite fiber bundle wire diameter: 280 microns) was prepared in the same manner as in Example 2. For the purpose of measuring the drug transport rate in the conductive composite fiber bundle portion of this catheter, the test was carried out by preparing a conductive composite fiber bundle for testing of this example. One end of the conductive composite fiber bundle of the catheter of this example is immersed in a chamber containing 1 mL of physiological saline containing 100 μM of Lucifer Yellow, which is a fluorescent substance, and the other end is physiologically containing no fluorescent substance. It was put into a dish containing 0.5 mL of saline. The water level in the chamber containing Lucifer Yellow was set to be 5 mm higher than the water level in the dish containing physiological saline containing no fluorescent substance. These were allowed to stand in a constant temperature room at 37 ° C., and the concentration of lucifer yellow contained in the physiological saline in the dish was measured on the 0th, 1, 2, 3, 4 and 7th day after installation.

  As Lucifer Yellow was transported from the chamber to the dish through the conductive conjugate fiber bundle, the concentration of Lucifer Yellow in the dish increased at a rate of 0.2 μM / day. From this result, it was found that Lucifer Yellow permeates (permeates and moves) the conductive conjugate fiber at a constant speed.

20, 20, 40, 50, 60, 100 Conductive conjugate fiber catheter 21 First base 23, 33 Second base 52 Ring-shaped electrode 62 Rod-shaped electrode 102 Lead wire 104 Electrode sections 22, 24, 42, 44, 106, 108 Conductor 110 Insulator 112 Conductive conjugate fiber 114 Fiber base material 116 Conductive polymer 9 Conductor tip exposed portion 10 Loop-shaped conductor tip exposed portion 11 Bar-shaped conductor tip exposed portion

Claims (5)

A catheter including a conductive conjugate fiber, comprising a lead wire and an electrode portion disposed at an end of the lead wire,
The lead wire is
(I) a conductor including a conductive composite fiber containing a conductive polymer; and (ii) an insulator including a fluorine-containing polyimide that covers the conductor;
The electrode part is
It looks containing the conductor of the (i) comprising a conductive composite fibers containing the conductive polymer,
The conductive composite fiber includes a conductive polymer in a fiber base material, the conductive polymer is impregnated and / or attached to a fiber base material, and the conductive polymer is a polycrystal. (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT-PSS),
The fluorine-containing polyimide of the insulator has a repeating unit represented by the following structural formula (1).

A catheter characterized by that. A catheter including a conductive conjugate fiber, comprising a lead wire and an electrode portion disposed at an end of the lead wire,
The lead wire is
(I) a conductor including a conductive conjugate fiber containing a conductive polymer; and
(Ii) Insulator containing fluorine-containing polyimide covering the conductor
Including
The electrode part includes the conductor (i) including a conductive conjugate fiber containing the conductive polymer,
The conductive composite fiber includes a conductive polymer in a fiber base material, the conductive polymer is impregnated and / or attached to a fiber base material, and the conductive polymer is a polycrystal. (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT-PSS),
The fluorine-containing polyimide of the insulator has a repeating unit represented by the following structural formula (2).

A catheter characterized by that. A catheter including a conductive conjugate fiber, comprising a lead wire and an electrode portion disposed at an end of the lead wire,
The lead wire is
(I) a conductor including a conductive conjugate fiber containing a conductive polymer; and
(Ii) Insulator containing fluorine-containing polyimide covering the conductor
Including
The electrode part includes the conductor (i) including a conductive conjugate fiber containing the conductive polymer,
The conductive composite fiber includes a conductive polymer in a fiber base material, the conductive polymer is impregnated and / or attached to a fiber base material, and the conductive polymer is a polycrystal. (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT-PSS),
The fluorine-containing polyimide of the insulator has a repeating unit represented by the following structural formula (3).

A catheter characterized by that. A catheter including a conductive conjugate fiber, comprising a lead wire and an electrode portion disposed at an end of the lead wire,
The lead wire is
(I) a conductor including a conductive conjugate fiber containing a conductive polymer; and
(Ii) Insulator containing fluorine-containing polyimide covering the conductor
Including
The electrode part includes the conductor (i) including a conductive conjugate fiber containing the conductive polymer,
The conductive composite fiber includes a conductive polymer in a fiber base material, the conductive polymer is impregnated and / or attached to a fiber base material, and the conductive polymer is a polycrystal. (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT-PSS),
The fluorine-containing polyimide of the insulator has a repeating unit represented by the following structural formula (4).

A catheter characterized by that. A catheter including a conductive conjugate fiber, comprising a lead wire and an electrode portion disposed at an end of the lead wire,
The lead wire is
(I) a conductor including a conductive conjugate fiber containing a conductive polymer; and
(Ii) Insulator containing fluorine-containing polyimide covering the conductor
Including
The electrode part includes the conductor (i) including a conductive conjugate fiber containing the conductive polymer,
The conductive composite fiber includes a conductive polymer in a fiber base material, the conductive polymer is impregnated and / or attached to a fiber base material, and the conductive polymer is a polycrystal. (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT-PSS),
The fluorine-containing polyimide of the insulator has a repeating unit represented by the following structural formula (5).

A catheter characterized by that.

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