JP2001058010A - Catheter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a medical catheter which is extremely little in the possibility of damaging the blood vessels, etc., is capable of preventing an odd feel and pain as far as possible and is excellent in safety and operability. SOLUTION: This catheter has a catheter body 1 of which at least the distal end side is formed of a shape memory metal having a shape memory characteristic at least at a biological temperature and not having superelasticity or pseudo- elasticity and an outer polymer layer 8 which coats the outer peripheral surface of the catheter body 1. A thermoplastic resin tube is connected to the front end of catheter body 1 and at least the base end side of the thermoplastic resin tube from the front end side of the catheter body 1 is coiled with a wire- like elastic material selected from a metallic wire, organic material wire and inorganic material wire or is braided like a mesh with this material or is formed with a reinforcing part by sticking the wire-like elastic material along an axial direction or combining these.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has an extremely low risk of damaging blood vessels, ureters, urethra, liver, bile and pancreatic ducts, etc. as compared with conventional catheters, and prevents discomfort and pain as much as possible. A medical catheter with excellent safety and operability, which can be smoothly introduced into a target site even in complicated and meandering fine blood vessels, ureters, urethra, liver, bile and pancreatic ducts, and foreign substances The present invention relates to a calculus capturing device and a catheter for capturing calculus and a foreign material removing and collecting device provided with an operation member having a distal end provided with a calculus capturing device capable of efficiently and reliably removing and collecting calculus.

[0002]

2. Description of the Related Art
Catheters inserted into blood vessels, ureters, etc. and used for examination, treatment, etc., for example, angiographic catheters, intravascular drug administration catheters, endovascular surgical catheters, ureteral stone catheters, transendoscopic retrograde Pancreatic cholangiography (ERC)
P) catheters and the like include a flexible polymer tube into which a guiding metal guide wire is inserted, a polyethylene tube in which a stainless wire is woven in a mesh shape, and a helical cut of a stainless tube. And those wrapped in a synthetic resin are known (JP-A-6-134034, JP-A-7-96037, etc.).

[0003] However, such a catheter is
It is difficult to insert into a complicated and meandering minute blood vessel or ureter and introduce it to the target site, and has all the characteristics required for catheters such as flexibility, suppleness, stiffness, and operability. Not something. For this reason, at present, a guide wire for guidance is always used together to supplement required characteristics.

[0004] Further, the catheter is as flexible as possible so as to minimize damage to the blood vessel and the inner wall of the ureter, particularly at the distal end thereof, and to allow the catheter to smoothly advance in the complicated and winding blood vessel and the ureter. What has excellent resilience is desired.

In this case, in the case of a conventional helical catheter in which a stainless steel wire or the like is braided at the center of the catheter or a stainless steel wire is cut, the tip of the helical catheter is several mm to several c.
m is formed mainly of a guiding polymer, and when the boundary between the polymer at the distal end and the metallic tip following the rear of the polymer hits a complicated and winding blood vessel wall or ureter wall, a flexible material is formed. The polymer tip can penetrate steep blood vessels and ureters, but when the border with the next advancing metal hits the vessel wall or ureter wall, the tip of the catheter May be broken or broken, causing pain or discomfort, or possibly damaging fragile blood vessels or the ureter.

[0006] A catheter having a main body and a distal end, and having a lumen therein, wherein at least the main body is formed of a superelastic metal tube has been proposed (Japanese Unexamined Patent Application Publication No. HEI 3 (1993) -1991). -188875).

However, in this catheter, since the superelastic metal tube has a superelastic effect or a pseudoelastic effect, the distal end of the catheter hits a part of a blood vessel or a ureter, and when it is deformed by an unreasonable force, a stress is generated. At the same time as the elimination, the super-elastic action immediately restores the original state, and the restoring force may cause damage to blood vessels and ureters (eg, rupture, perforation, dissection, etc. of blood vessels and ureters). Like the above-mentioned helical catheter, there is a risk of injuries on the wall of the blood vessel or the ureter, which are complicated and tortuous.

On the other hand, catheters for removing and collecting foreign substances and catheters for capturing calculi such as kidneys and ureters include:
There are various proposals in which an operating member having a foreign matter collection / removal means and a calculus capturing means at the tip is inserted through the catheter lumen (Japanese Patent Application Laid-Open No. S61-115550).

[0009] These catheters for removing and collecting foreign matters and the catheter for capturing calculi have a strong main body made of a shape memory alloy having superelasticity or pseudoelasticity and have a strong restoring force. The operation wire (operation member) behind the means and the calculus capturing means is also a reaction force,
Strong repulsion force and lack of flexibility make it difficult to insert a catheter smoothly and carry foreign matter removal and collection means and stone capture means to the target site when applied to a complicated and meandering fine ureter. At present, the effects of the foreign matter removal / recovery means and the calculus capturing means have not been sufficiently and effectively extracted, and at present, good foreign matter removal / recovery results and calculus capture results have not been achieved.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems. First, there is no step at the connecting portion between the leading thermoplastic resin tube and the catheter body. It is an object of the present invention to provide a catheter which can prevent as much as possible damage to the upper blood vessel, the ureter, the pancreatic bile duct, and the like.

Second, the present invention eliminates the superelastic effect or the pseudoelastic effect while leaving the shape memory effect at least at the distal end side of the catheter main body, and has a rigid base end side of the catheter main body. An object of the present invention is to provide a catheter which has excellent flexibility, flexibility and sufficient stiffness, can be operated without a guide wire for guidance, and is excellent in safety and operability.

Further, in the present invention, thirdly, in the first and second catheters, an operation member having a foreign matter removing and collecting means and a calculus capturing means at a distal end portion thereof is inserted into the catheter lumen, and the operation member is used as the operation member. By forming at least the distal end side of a metal having shape memory at least at a biological temperature and having no superelasticity or pseudoelasticity (hereinafter referred to as a shape memory alloy), a complicated and meandering fine ureter It is an object of the present invention to provide a catheter for removing and collecting foreign matters and capturing calculi that can safely and reliably remove and collect foreign matters and capture calculi.

[0013]

Means for Solving the Problems The present inventor has made intensive studies to achieve the above object, and as a result, in a catheter having a leading thermoplastic resin tube attached to the distal end of a catheter body, a thermoplastic resin tube is provided. In addition, in this case, at least the distal end side of the catheter main body retains shape memory at least at a biological temperature by heat treatment or the like, and becomes superelastic or pseudoelastic. It was found that the lost catheter was optimal in terms of safety and operability.

That is, at least the distal end has a catheter body made of a shape memory metal having shape memory at least at a living body temperature and not having superelasticity or pseudoelasticity, and an outer peripheral surface of the catheter body. An outer polymer layer to be coated, and a thermoplastic resin tube connected to the distal end of the catheter main body, and at least a proximal end side of the thermoplastic resin tube from the distal end side of the catheter main body, particularly the catheter main body and the thermoplastic resin tube. The connection portion with the resin tube and the vicinity thereof are wound from the outside or inside with a linear elastic material selected from a metal wire, an organic wire and an inorganic wire in a coil shape or knitted in a mesh shape, or the linear elastic material is stretched in the axial direction. Attached along or in combination to form a reinforcement, the catheter connection and its vicinity are still in place. Unprecedented flexibility, flexibility is given, even if it is a complicated and meandering fine blood vessel or ureter, it can follow the shape sufficiently, and the catheter can be guided smoothly and reliably to the target site, there is no step, It has been found that a catheter can be obtained in which the feeling of discomfort and pain is extremely low and the inside of a blood vessel or ureter which is vulnerable in operation is not damaged.

In addition to the above-mentioned effects of the present invention, in addition to the formation of the reinforcing portion, at least the distal end side of the catheter body has shape memory at least at a biological temperature,
And it is further doubled by being formed of a shape memory metal having no superelasticity or pseudoelasticity, and these are combined,
It has been found that an optimal medical catheter for examination and treatment of blood vessels, ureters, pancreaticobiliary ducts and the like can be obtained.

In more detail, the shape memory alloy used for the catheter body, for example, a Ni-Ti alloy, has a superelastic effect (also called a pseudoelastic effect) and a shape accompanying the inverse transformation of the thermoelastic martensitic transformation. Memory effect 2
It is known to have two properties. The shape memory effect refers to a property in which when an Ni-Ti alloy undergoes apparent plastic deformation, the alloy returns to its initial shape when heated to a so-called reverse transformation temperature. On the other hand, the superelastic effect or pseudoelastic effect means that when a stress load is applied to a Ni-Ti alloy at a temperature equal to or higher than the inverse transformation point temperature to give an apparent plastic deformation, the shape of the alloy is restored at the same time as the stress is removed. It is the nature to do.

The present inventor has proposed that such a shape memory alloy 2
Among the two properties, in a catheter to be inserted into a fragile and tortuous site such as a blood vessel, it is extremely advantageous to have a shape memory effect at the body temperature, but it has a superelastic effect (or pseudoelastic effect) at the body temperature. I found that things worked rather disadvantageously.

In other words, when a catheter is inserted into a complicated, meandering fragile blood vessel or the like, if a catheter made of a shape memory alloy tube having the above two properties is used, the tip of the complicated meandering blood vessel wall, etc. If hit,
Even if it deforms and the tip can enter a steep blood vessel, etc., it has a strong restoring force due to the superelastic effect (or pseudoelastic effect). A strong force may be applied to cause vascular or ureteral damage (eg, rupture of blood vessels or ureter, perforation, dissection, etc.).

Therefore, as a result of further diligent studies by the present inventors, heat treatment or the like of at least the distal end side of the catheter body made of a shape memory alloy causes the shape memory alloy to lose its superelastic effect or pseudoelastic effect at living body temperature. When a certain amount of stress is applied to the catheter in a blood vessel or the like, the catheter is easily crushed or bent, and the restoring force does not act immediately, so that the risk of damaging the blood vessel wall and the like is reduced. Since the shape memory effect of the alloy remains sufficiently (shape memory alloy), even if the catheter is crushed or broken due to excessive force applied in blood vessels or ureter, it will gradually recover in its natural state. It was found that the shape was restored.

Here, the existence regions exhibiting the superelastic effect and the shape memory effect do not always coincide with each other.
(B) at the set temperature showing the superelastic effect and the living body temperature
The set temperature indicating the shape memory effect is different. (A) If the set temperature showing the superelastic effect is set to 90 ° C., the heat treatment conditions are set so as to be in a soft state around 37 ° C. and to exhibit the shape memory effect. If (A)
Assuming that the set temperature showing the superelastic effect is around 37 ° C.,
(B) The set temperature indicating the shape memory effect is lower than this, which does not meet the purpose of the present invention. In this case, (A)
Between the set temperature indicating the superelastic effect and (B) the set temperature indicating the shape memory effect, there is a region showing the superelastic effect and also showing the shape memory effect. When the catheter is deformed at the living body temperature, when the deforming force is released, the original shape is restored.However, whether this restoring force is a superelastic effect or a shape memory effect is restored, 0.3 seconds. When the restoration is performed in less than 30 seconds, it is considered that the superelastic effect is acting strongly. There is a possibility that the inside of the ureter may be damaged.

Here, in the present invention, "the body temperature does not have superelasticity or pseudoelasticity" means that a set temperature indicating superelasticity and a region exhibiting superelastic effect and exhibiting shape memory effect are defined as biological temperature. Good to be in a higher temperature range. FIG.
As shown in (A), at least the distal end side (at least a portion of 5 mm from the distal end, particularly a portion of 30 cm from the distal end) of the catheter body 1 to which one end is fixed is placed at the biological temperature (33 to 42 ° C., preferably 35 to 42 ° C.). 38 [deg.] C.) at an angle [alpha] of 30 to 90 degrees, preferably 45 to 90 degrees (FIG. 1 (B)), when the deformation force is released, instantaneous (rapid) due to superelasticity or pseudoelasticity. Instead of returning, it returns slowly (gradually) with shape memory (Fig. 1
(C)). This restoring force is expressed in time as 0.3
Seconds or more, preferably 0.5 seconds or more, more preferably 1 second or more, still more preferably 1.5 seconds or more, and most preferably 2 seconds or more.
Means more than a second.

Furthermore, as a result of the present inventor's further intense study of the shape memory effect of the catheter body from other angles other than specifying the time, it was found that "there is no superelasticity or pseudoelasticity at the body temperature". It has been found that it can be explained by the yield load, the recovery load, and the residual strain in a predetermined three-point bending test.

That is, as shown in FIG. 2, a metal tube T having an outer diameter of 875 .mu.m and an inner diameter of 750 .mu.m having a superelastic effect and a shape memory effect or having only a shape memory effect is supported on a jig by supporting points a to d. According to the following measurement conditions, the yield stress at the time of 1 mm displacement of each measurement site shown in FIG. 3, the recovery load, the residual strain was obtained from the residual displacement after the load was released, the yield load and the recovery load The relationship shown in FIGS. 4 to 6 is recognized between the residual strain.

<Measurement conditions> Test speed: 2 mm / min Punch tip shape: φ5 mm Support point shape (ad): φ6 mm Distance between support points (ab): 18 mm Distance between support points (cd): 14 mm Punch displacement ： 2mm Measurement temperature ： 37 ± 1 ℃

That is, from FIG. 4, the yield load and the recovery load show a substantially proportional relationship when the yield load is about 5.9 N or more.
FIG. 5 shows that the yield load and the residual strain show a substantially inverse proportional relationship when the yield load is 8.8 N or less, that is, as the yield load increases, the recovery load increases and the residual strain decreases. Further, when the yield load is 8.8 N or less, the recovery load is 2.9 N or less, and the residual strain is 0.2 mm or more, the deformed state can be maintained, and it is possible to prevent a strong return at the time of displacement, that is, superelasticity. No effect or pseudoelastic effect was found.

In fact, the present inventor examined that the yield load, the recovery load, and the residual strain in the three-point bending test on the distal end side of the catheter body (at least a portion 5 mm from the distal end, particularly a portion 30 cm from the distal end). If the above range is not satisfied, the superelastic effect or the pseudoelastic effect acts strongly, and it is recognized that the strong restoring force may possibly damage the inside of the blood vessel or ureter during catheter operation. That is, in the present invention, “having no superelasticity or pseudoelasticity at the biological temperature” means that a set temperature at which the superelasticity is exhibited, and a temperature range at which the region exhibiting the superelastic effect and exhibiting the shape memory effect are higher than the biological temperature. When at least the distal end side of the catheter body (at least a portion up to 5 mm from the distal end, in particular, a portion up to 30 cm from the distal end) is deformed at least at the body temperature, when the deforming force is released (or during operation of the catheter) Release your hand),
It means that the recovery requires 0.3 seconds or more, preferably 0.5 seconds, more preferably 1 second or more, further preferably 1.5 seconds or more, and most preferably 2 seconds or more. In this case, as described above, at least the distal end of the catheter body has a yield load of 8.8 N or less and a recovery load of 2 when a three-point bending test is performed using a tube having an outer diameter of 875 μm and an inner diameter of 750 μm. It is preferable to use a metal material having a residual strain of 0.9 mm or less and a residual strain of 0.2 mm or more.

More specifically, the preferred ranges of the yield load, the recovery load, and the residual strain in the above-described three-point bending test vary depending on the inner and outer diameters of the catheter body, and are preferably the following ranges.

<Case where the inner diameter of the catheter body is 800 μm or more and the outer diameter is 950 μm or more> (i) Yield load is 10.8 N or less, preferably 7.4 N
It is preferably 6.4 N or less, more preferably 5.4 N or less, and most preferably 4.4 N or less. (Ii) The recovery load is 3.9N or less, preferably 2.9N
It is preferably 2.0 N or less, more preferably 1.0 N or less. (Iii) The residual strain is 0.2 mm or more, preferably 0.1 mm or more.
It is preferably at least 5 mm, more preferably at least 0.9 mm, even more preferably at least 1.2 mm.

<Inner diameter of catheter body is 600 to 800>
μm and outer diameter of 700 to 950 μm> (i) Yield load is 8.8 N or less, preferably 6.4 N or less, more preferably 5.4 N or less, and even more preferably 4.4.
N or less, most preferably 2.9 N or less. In this case, the lower limit is not particularly limited, but is preferably 0.1 N or more. (Ii) The recovery load is 2.9N or less, preferably 1N or less, more preferably 0.5N or less. In this case, the lower limit is not particularly limited, but is preferably 0N. (Iii) The residual strain is 0.2 mm or more, preferably 0.1 mm or more.
It is 5 mm or more, more preferably 0.9 mm or more, and still more preferably 1.2 mm or more. In this case, the upper limit is not particularly limited, but is preferably 1.8 mm or less.

<Case where the inner diameter of the catheter body is 250 μm or more and less than 600 μm, and the outer diameter is 350 μm or more and less than 700 μm> (i) The yield load is 6.9 N or less, preferably 4.9 N or less, more preferably 3.9 N or less. And more preferably 2.
9N or less, most preferably 2N or less, where
The lower limit is not particularly limited, but is preferably 0.1 N or more. (Ii) The recovery load is preferably 2N or less, preferably 1N or less, more preferably 0.5N or less, and most preferably 0.1N or less. (Iii) The residual strain is 0.2 mm or more, preferably 0.1 mm or more.
It is preferably at least 5 mm, more preferably at least 0.9 mm, even more preferably at least 1.2 mm.

<Case where the inner diameter of the catheter body is less than 250 μm and the outer diameter is less than 350 μm> (i) The yield load is preferably 2 N or less, preferably 1 N or less, more preferably 0.9 N or less. (Ii) The recovery load is preferably 1 N or less, preferably 0.6 N or less, more preferably 0.1 N or less. (Iii) The residual strain is 0.2 mm or more, preferably 0.1 mm or more.
It is preferably at least 5 mm, more preferably at least 0.9 mm, even more preferably at least 1.2 mm.

As described above, when the yield load, the recovery load, and the residual strain in the three-point bending test on at least the distal end side (at least a portion of 5 mm from the distal end, particularly, a portion of 30 cm from the distal end) of the catheter main body fall below the above ranges. The distal end side of the main body becomes too soft, and the rigidity (strongness) of the proximal end side is weakened, which may cause a problem in operability. On the other hand, when the yield load, the recovery load, and the residual strain exceed the above ranges, the recovery force on the distal side of the catheter body is too strong, causing damage to blood vessels, ureters, and the like, and the rigidity on the proximal side is strong. This may cause problems in safety and operability.

The yield load when a three-point bending test is performed on the proximal end side (at least a portion from the proximal end to 5 mm) of the catheter body using an outer diameter of 875 μm and an inner diameter of 750 μm is 8.9 N or more. The recovery load is 3.0 N or more, the residual strain is less than 0.2 mm, and has sufficient rigidity. In this case, the yield load, the recovery load, and the residual strain between the distal end side and the proximal end side of the catheter body can be appropriately set according to operability and the like.

The catheter of the present invention is essentially a shape memory effect, at least at the body temperature, and has no superelastic effect or pseudoelastic effect.
In contrast, in the superelastic metal tube or the shape memory alloy tube catheter body described in JP-A-3-188875, the restoring force after deformation is less than 0.3 seconds, and the yield load is considerably large (that is, the yield load is large). , A large recovery load), and instantaneously recovers due to the superelastic effect or the pseudoelastic effect. The catheter body of the present invention applies only shape memory and does not exhibit the superelastic effect or pseudoelastic effect of a conventional catheter of this type.

As described above, in the catheter of the present invention, the guiding thermoplastic resin tube is attached to the distal end of the catheter main body without any level difference in an extremely flexible state, and at least the distal end side of the catheter main body has a shape memory effect. Eliminating the superelastic effect or pseudoelastic effect, that is, when at least the distal end of the catheter body is deformed at the body temperature, it takes 0.3 seconds or more to recover, especially at least the distal end of the catheter body 875μ diameter
m, the yield load when performing a three-point bending test using a tube having an inner diameter of 750 μm is 8.8 N or less, and the recovery load is 2.9 N.
Hereinafter, by using a metal material having a residual strain of 0.2 mm or more, the risk of damaging blood vessels and ureters is extremely small as compared with conventional catheters, and discomfort and pain can be prevented as much as possible. It is possible to obtain a medical catheter excellent in safety and operability that can smoothly introduce even a tortuous minute blood vessel or ureter to a target site.

The catheter disclosed in JP-A-3-188875 uses a super-elastic metal body such as a Ti-Ni alloy as a super-elastic metal tube.
Since it has not only a shape memory effect but also a superelastic effect and strong elasticity (returnability to the original shape), there is a possibility that the inside of a blood vessel or ureter may be erroneously damaged during operation. In other words, conventionally, it was thought that properties such as superelasticity and pseudoelasticity were necessary for catheters and guidewires. However, according to actual studies by the present inventors, superelasticity and pseudoelasticity Then, when they release their hands due to this elasticity, they have a strong property of immediately returning to their original state, and found that there is a problem that if excessive force is applied to blood vessels and ureters, blood vessel damage and ureteral damage may occur. .

Accordingly, the present invention provides the following catheter. Claim 1: at least the distal end side has a shape memory at least at a biological temperature, and a catheter body formed of a shape memory metal having no superelasticity or pseudoelasticity,
An outer polymer layer covering the outer peripheral surface of the catheter body, and a thermoplastic resin tube connected to a distal end of the catheter body, and at least a proximal end side of the thermoplastic resin tube from the distal end side of the catheter body. A metal wire, an organic wire and an inorganic wire, wound in a coil shape or knitted in a mesh shape with a linear elastic material selected from an inorganic wire, or affixed the linear elastic material along the axial direction, or a combination thereof to form a reinforcing portion. A catheter characterized in that it is formed. In a preferred embodiment, the inner polymer layer is formed by applying a polymer to the inner surface of the catheter body and the thermoplastic resin tube. In a preferred embodiment, at least the proximal end of the thermoplastic resin tube from the distal end of the catheter body is coiled or knitted from outside with a linear elastic material selected from a metal wire, an organic wire and an inorganic wire. The catheter according to claim 1, wherein a reinforcing portion is formed by attaching a linear elastic material along the axial direction or by combining them. In a preferred embodiment, the distal end of the catheter body and the proximal end of the thermoplastic resin tube are formed in a tapered shape, and the tapered connecting portion and the vicinity thereof are linearly selected from the outside from a metal wire, an organic wire and an inorganic wire. 4. The reinforcing portion according to claim 1, wherein the reinforcing portion is formed by winding in a coil shape, knitting in a mesh shape, sticking a linear elastic material along an axial direction, or combining them. catheter. Claim 5: The connecting portion between the catheter body and the thermoplastic resin tube and the vicinity thereof are wound in a coil shape or knitted in a mesh shape from the inside with a linear elastic material selected from a metal wire, an organic wire and an inorganic wire, or The reinforcing part is formed by attaching a linear elastic material along the axial direction or by combining them.
Item 7. The catheter according to item 1. [6] The catheter according to any one of [1] to [5], wherein an X-ray contrast agent is contained in the thermoplastic resin tube. [7] The catheter according to any one of [1] to [6], wherein when at least the distal end side of the catheter body is deformed at the biological temperature, it takes 0.3 seconds or more to recover. Claim 8: At least the distal end of the catheter body is subjected to a three-point bending test using a tube having an outer diameter of 875 μm and an inner diameter of 750 μm, the yield load is 8.8 N or less, the recovery load is 2.9 N or less, and the residual load is The catheter according to any one of claims 1 to 7, wherein the catheter is formed of a metal material having a strain of 0.2 mm or more. In a ninth aspect, at least the distal end side of the catheter body is formed of the shape memory metal, and the remaining portion of the catheter body has shape memory at least at a biological temperature and has superelasticity or pseudoelasticity. 9. The catheter according to claim 1, wherein the catheter is formed of a memory alloy. [10] The catheter according to any one of [1] to [9], wherein a tip of the shape memory metal portion is formed in a tapered shape. [11] The catheter according to any one of [1] to [10], wherein the distal end of the shape-memory metal portion is shape-memory so as to be curved at a biological temperature within a radius of curvature of 0 to 200 mm. In a twelfth aspect of the present invention, the shape-memory metal part is provided at a living body temperature of 0 to 1.
The shape memory is configured to be bent by 20 degrees.
The catheter according to any one of the preceding claims. Claim 13: The shape memory metal is Ni-Ti having lost superelasticity or pseudoelasticity at least at a biological temperature.
The catheter according to claim 1, wherein the catheter is a Fe-based or Cu-based shape memory alloy. [14] The catheter according to any one of [2] to [13], wherein an inner metal layer containing no Ni is formed between at least the inner peripheral surface of the shape memory metal portion of the catheter body and the inner polymer layer. [15] The catheter according to any one of [1] to [14], wherein an outer metal layer is formed between at least an outer peripheral surface of the shape memory metal portion of the catheter body and the outer polymer layer. Claim 16: The catheter according to claim 14 or 15, wherein a monopolar high-frequency current is caused to flow through the thermoplastic resin tube using the inner or outer metal layer of the catheter body so that the tube can be melt-cut. Claim 17: An inner metal layer not containing Ni is formed between the inner peripheral surface of the catheter body and the inner polymer layer,
An outer metal layer is formed between the outer peripheral surface of the catheter body and the outer polymer layer, and a bipolar high-frequency current is applied to the thermoplastic resin tube by using the inner and outer metal layers to melt and cut the tube. Item 15. The catheter according to any one of items 2 to 14. Claim 18: At least the distal end side of the catheter main body is formed of a shape memory metal having shape memory at least at a biological temperature and not having superelasticity or pseudoelasticity, and at least the distal end side of the catheter main body. When deformed at body temperature, it takes 0.3 seconds or more to recover, and at least the distal end of the catheter body has an outer diameter of 8 mm.
It was formed of a metal material having a yield load of 8.8 N or less, a recovery load of 2.9 N or less, and a residual strain of 0.2 mm or more when a three-point bending test was performed using a pipe having a diameter of 75 μm and an inner diameter of 750 μm. A catheter characterized by the above-mentioned. Claim 19: At least the distal end side of the catheter main body is formed of a shape memory metal that has shape memory at least at a biological temperature and does not have superelasticity or pseudoelasticity, and at least the distal end side of the catheter main body. When deformed at body temperature, it takes 0.3 seconds or more to recover, and at least the distal end of the catheter body has an outer diameter of 8 mm.
A catheter formed of a metal material having a yield load of 8.8 N or less, a recovery load of 2.9 N or less, and a residual strain of 0.2 mm or more when a three-point bending test is performed using a tube having a diameter of 75 μm and an inner diameter of 750 μm. The base body from the proximal end to the distal end of the catheter body is wound in a coil shape or knitted in a mesh shape with a linear elastic material selected from a metal wire, an organic wire and an inorganic wire, or is made of a linear elastic material. A catheter which is reinforced by being attached along a direction or by combining them. [20] The catheter according to any one of [1] to [19], wherein an operating member having a calculus capturing unit or a foreign matter removing and collecting unit at a distal end thereof is inserted into the catheter lumen. In the twenty-first aspect, at least the distal end side of the operation member is formed of a shape-memory metal that has shape memory at least at a biological temperature and does not have superelasticity or pseudoelasticity. catheter. [Claim 22] The catheter according to claim 21, wherein when at least the distal end side of the operation member is deformed at the living body temperature, it takes 0.3 seconds or more to recover.

According to the catheter of the present invention, the thermoplastic resin tube is connected to the distal end of the catheter body directly or via the inner polymer layer, and at least the proximal end side of the thermoplastic resin tube is connected from the distal end side of the catheter main body. In particular, the connecting portion and the vicinity thereof are wound in a coil shape or knitted in a mesh shape with a linear elastic material selected from a metal wire, an organic wire and an inorganic wire, or the linear elastic material is stuck along the axial direction or By forming a reinforcing portion by combining, conventionally, even if the catheter body is extremely flexible, if the catheter is introduced into a meandering blood vessel, ureter, or the like, it will bend at the connecting portion, causing a step, It is possible to prevent discomfort, pain, and possibly damage to blood vessels and ureters as much as possible. Rikune' was fine blood vessels and a ureter, etc. also sufficiently follow give, in which the catheter can be reliably guided to the target site.

That is, since the connecting portion between the metallic catheter main body and the thermoplastic resin tube and the vicinity thereof are protected by the formation of the reinforcing portion, the connecting portion sharply bends and the distal end side of the catheter main body becomes close to a blood vessel or the like. Without hitting strongly
The bending stress does not directly act on the connecting portion at the branching point of a blood vessel or the like, but can smoothly advance in a complicated winding blood vessel or ureter so as to be buffered in the reinforcing portion and gradually curved in the reinforcing portion. Things.

The above operation and effect of the present invention are as follows. At least the distal end side of the catheter main body is formed of a shape memory metal which has shape memory at least at body temperature and does not have superelasticity or pseudoelasticity. That the shape memory effect requires at least 0.3 seconds to recover when at least the distal end of the catheter body is deformed at the body temperature, and that at least the distal end of the catheter body has an outer diameter of 875 μm and an inner diameter of 750 μm When a three-point bending test is carried out using a tube having a yield load of 8.8 N or less, a recovery load of 2.9 N or less, and a residual strain of 0.2 mm or more, they are formed of a metal material. Together, they can be achieved more reliably.

That is, at least the distal end side of the catheter main body is formed of a shape memory metal that has shape memory at least at a biological temperature and does not have superelasticity or pseudoelasticity. There is no vascular damage or ureteral damage based on elasticity or pseudoelasticity, and the shape can be adjusted to the shape of the blood vessel or ureter at the insertion target site by the shape memory effect.

In this case, in particular, by forming the distal end portion of the shape memory metal portion in a tapered shape and making it thinner than the proximal end side, the flexibility increases more as the catheter body moves toward the distal end, and the insertion target site is formed. It can proceed more smoothly according to the shape of blood vessels, ureters and the like. Therefore, since the distal end portion of the catheter body is flexible as described above, when a thermoplastic resin tube (lead tube) is attached to the distal end of the catheter body, the flexible lead tube is used in a target steep blood vessel or ureter. As it enters, the leading end of the catheter body along with the leading tube is broken at the connecting part, and the distal end of the catheter body is broken at the connecting part between the leading tube and the catheter body and the vicinity thereof. It is guided smoothly and steeply into blood vessels and ureters without generating.

In this case, R (R) of about 0 to 200 mm at the living body temperature is applied to the tip of the shape memory metal part.
Shape memory so as to have
By storing the shape so that it bends at ~ 120 °,
It can be guided more smoothly and more easily in steep blood vessels and ureters.

The shape memory effect is necessary especially in a blood vessel or a ureter in which a strongly bent loop is wound at a living body temperature after a catheter is inserted. When the catheter is bent to some extent, the distal end thereof does not damage blood vessels and ureters, and is smoothly guided to the target blood vessels and ureters. In the present invention, it is important to eliminate superelasticity and pseudoelasticity at least on the distal end side of the catheter body, the distal end hits a part of a blood vessel or ureter,
When a reaction force and repulsion force occur like a conventional superelastic metal tube catheter, it immediately returns to its original state, and it is restored with shape memory so that it does not cause vascular or ureteral damage. However, in this case, since there is no reaction force or repulsive force, it deforms to its shape on the spot (in the blood vessel or ureter) until there is no excessive force, pulls the catheter, and when there is no excessive force, the original Restores slowly to the shape of.

In addition, by making the proximal end side of the catheter body relatively rigid, even if the distal end side of the catheter body is deformed, it is intended to eliminate blood vessel damage and ureteral damage during the catheter introduction operation. The catheter can be smoothly guided to a predetermined site without abrupt restoration and with the strength (rigidity) at the proximal end side without any trouble. (33
At about 42 ° C., preferably 35 to 38 ° C.).

In addition, by providing the rigidity to the proximal end side of the catheter main body as described above, it is possible to omit the use of the leading guide wire from this characteristic.

Further, by forming a metal layer having excellent conductivity on the inner or outer peripheral surface or the inner or outer peripheral surface of the catheter body, not only protection of the inner and outer peripheral surfaces but also melting and cutting of the thermoplastic resin tube can be performed. Detachment of the connecting member of the medical wire having the indwelling member, or PVA,
In the case of bonding with EVA or the like, the present invention can be applied to the case where this connecting polymer is detached.

Further, in the catheter for removing and collecting foreign matter and capturing calculus of the present invention, at least the distal end side of the catheter body has shape memory at least at a biological temperature and has superelasticity or pseudoelasticity as described above. Using a catheter formed of a non-shape memory metal, an operating member having a foreign matter removal and recovery unit and a calculus capturing unit at the tip is inserted into the catheter lumen, and this operation member is also inserted into the same shape memory metal as described above. By forming by this, an excellent foreign matter removal and collection effect and a calculus capturing effect are exhibited.

That is, the conventional foreign matter removal / collection and calculus capture catheter focuses on variously improving the performance of the foreign matter removal / collection means and the calculus capture means. Since the performance of the operating member following the capturing means has not been sufficiently considered, it is difficult to smoothly transport the foreign matter removing and collecting means and the calculus capturing means to the target site. Performance was not fully exploited.

Therefore, the catheter body of the catheter for removing and collecting foreign matter and capturing calculi is made of a shape memory metal at least at the distal end side which has a shape memory at least at a living body temperature and has no superelasticity or pseudoelasticity. And at least the distal end of the catheter body is deformed at least at the body temperature, so that the catheter body can be restored to a minimum temperature.
It takes 3 seconds or more, and at least the distal end of the catheter body has a yield load of 8.8 N or less and a recovery load of 2.9 N when a three-point bending test is performed using a tube having an outer diameter of 875 μm and an inner diameter of 750 μm. Hereinafter, the residual strain is formed of a metal material of 0.2 mm or more, more preferably, a thermoplastic resin tube is connected to the distal end of the catheter body, and at least the connection part and the vicinity thereof are metal wires and organic wires from the inside and outside. And a coil formed of a linear elastic material selected from inorganic wires or knitted in a mesh shape, or a linear elastic material is applied along the axial direction or a combination thereof, and a catheter formed with a reinforcing portion is used. When the operation member following the foreign matter removal / recovery means or the calculus capture means is deformed at the temperature of the living body, the shape memory metal, particularly at least the distal end side, is deformed. By forming the ureter taking 0.3 seconds or more to recover, even if it is a complicated and meandering fine ureter or the like, it does not damage the inside of the ureter, etc. Can be reliably carried, the performance of the foreign matter removing and collecting means and the stone capturing means can be sufficiently brought out, and safe and high foreign matter removing and collecting results and stone capturing results can be achieved.

[0051]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to the drawings. The catheter of the present invention has a catheter body at least on the distal end side, which has shape memory at least at a biological temperature, and is formed of a shape memory metal having no superelasticity or pseudoelasticity, and an outer peripheral surface of the catheter body. And a thermoplastic resin tube connected to the distal end of the catheter main body, and at least a proximal end side of the thermoplastic resin tube from the distal end side of the catheter main body to a metal wire and an organic wire. And a linear elastic material selected from inorganic wires, wound in a coil shape or knitted in a mesh shape, or pasted along the linear elastic material along the axial direction, or a combination thereof to form a reinforcing portion.

The catheter body has a shape memory at least at the distal end side at least at a biological temperature (33 to 42 ° C., preferably 35 to 38 ° C.), but does not have superelasticity or pseudoelasticity. The one formed of metal is used.

As described above, in the present invention, "having no superelasticity or pseudoelasticity at the living body temperature" means that when the deforming force is released at the living body temperature, it is considered that the original shape cannot be restored. It takes 3 seconds or more, preferably 0.5 seconds or more, more preferably 1 second or more, still more preferably 1.5 seconds or more, and most preferably 2 seconds or more, and yield load and recovery load in a three-point bending test. And residual strain.

As described above, in the three-point bending test, as shown in FIG. 2, the pipe T is set at the fulcrums a to d, and the yield load and the recovery load at the time of displacement of 1 mm under predetermined measurement conditions. Is measured, and a residual strain is obtained from a residual displacement amount after the load is released.

In this case, at least the distal end side (at least a portion of 5 mm from the distal end) of the catheter body is
When a three-point bending test is performed using a tube having an outer diameter of 875 μm and an inner diameter of 750 μm, a metal material having a yield load of 8.8 N or less, a recovery load of 2.9 N or less, and a residual strain of 0.2 mm or more is used. Is preferred.

More specifically, the preferred ranges of the yield load, the recovery load, and the residual strain in the above-described three-point bending test are as follows:
It varies depending on the inner diameter and outer diameter of the catheter main body, and is preferably in the following range.

<When the inner diameter of the catheter body is 800 μm or more and the outer diameter is 950 μm or more> (i) The yield load is 10.8 N or less, preferably 7.4 N
It is preferably 6.4 N or less, more preferably 5.4 N or less, and most preferably 4.4 N or less. (Ii) The recovery load is 3.9N or less, preferably 2.9N
It is preferably 2.0 N or less, more preferably 1.0 N or less. (Iii) The residual strain is 0.2 mm or more, preferably 0.1 mm or more.
It is preferably at least 5 mm, more preferably at least 0.9 mm, even more preferably at least 1.2 mm.

<The inner diameter of the catheter body is 600 to 800
μm and outer diameter of 700 to 950 μm> (i) Yield load is 8.8 N or less, preferably 6.4 N or less, more preferably 5.4 N or less, and even more preferably 4.4.
N or less, most preferably 2.9 N or less. In this case, the lower limit is not particularly limited, but is preferably 0.1 N or more. (Ii) The recovery load is 2.9N or less, preferably 1N or less, more preferably 0.5N or less. In this case, the lower limit is not particularly limited, but is preferably 0N. (Iii) The residual strain is 0.2 mm or more, preferably 0.1 mm or more.
It is 5 mm or more, more preferably 0.9 mm or more, and still more preferably 1.2 mm or more. In this case, the upper limit is not particularly limited, but is preferably 1.8 mm or less.

<Case where the inner diameter of the catheter body is 250 μm or more and less than 600 μm, and the outer diameter is 350 μm or more and less than 700 μm> (i) Yield load is 6.9 N or less, preferably 4.9 N or less, more preferably 3.9 N or less. And more preferably 2.
9N or less, most preferably 2N or less, where
The lower limit is not particularly limited, but is preferably 0.1 N or more. (Ii) The recovery load is preferably 2N or less, preferably 1N or less, more preferably 0.5N or less, and most preferably 0.1N or less. (Iii) The residual strain is 0.2 mm or more, preferably 0.1 mm or more.
It is preferably at least 5 mm, more preferably at least 0.9 mm, even more preferably at least 1.2 mm.

<Case where the inner diameter of the catheter body is less than 250 μm and the outer diameter is less than 350 μm> (i) The yield load is 2N or less, preferably 1N or less, more preferably 0.9N or less. (Ii) The recovery load is preferably 1 N or less, preferably 0.6 N or less, more preferably 0.1 N or less. (Iii) The residual strain is 0.2 mm or more, preferably 0.1 mm or more.
It is preferably at least 5 mm, more preferably at least 0.9 mm, even more preferably at least 1.2 mm.

When the yield load, the recovery load and the residual strain at least on the distal side of the catheter body are below the above ranges, the distal side of the catheter body becomes too soft and the rigidity on the proximal side of the catheter body becomes weak. A problem may arise in operability. On the other hand, if the yield load, the recovery load, and the residual strain do not satisfy the above ranges, the recovery force (restoring force) on the distal side of the catheter body is too strong, causing damage to blood vessels, ureters, and the like, or rigidity on the proximal side ( Strength) is too strong
A problem may arise in operability.

The yield load when the three-point bending test is performed on the proximal end side (at least a portion from the proximal end to 5 mm) of the catheter body using an outer diameter of 875 μm and an inner diameter of 750 μm is 8.9 N or more. The recovery load is 3.0 N or more, the residual strain is less than 0.2 mm, and has sufficient rigidity. In this case, the yield load, the recovery load, and the residual strain between the distal end side and the proximal end side of the catheter body can be appropriately set according to operability and the like.

In the present invention, the entirety of the tubular catheter body may be formed of the above-mentioned shape memory metal, and only the distal end side of the tubular catheter body is formed of the above-mentioned shape memory metal, and at least the remaining portion is formed. It can be formed of a shape memory alloy having superelasticity or pseudoelasticity at the temperature of a living body and having superelasticity or pseudoelasticity, or a metal having no shape memoryability such as stainless steel in some cases.

Here, the shape-memory metal portion should be at least a portion up to about 15 cm from the most distal end of the catheter body, more preferably up to about 30 cm, and even more preferably up to about 180 cm. Recommended for more effectively achieving the objects of the invention.

The catheter body of the present invention is made of Ni—Ti
A shape-memory alloy such as a Fe-based alloy, a Cu-based alloy, or a Cu-based alloy can be formed into a shape-memory alloy by heat treatment or the like.
Such shape memory alloys include Ni-Ti alloy, N
i-Ti-Co alloy, Ni-Ti-Fe alloy, Ni-T
i-Mn alloy, Ni-Ti-Cr alloy, Ni-Ti-V
Alloy, Ni-Ti-Al alloy, Ni-Ti-Nb alloy,
Cu-Zn alloy, Cu-Zn-Be alloy, Cu-Zn
-Si alloy, Cu-Zn-Sn alloy, Cu-Zn-Ga
Alloys, Cu-Al-Ni-based alloys, Cu-Al-Zn-based alloys, and the like can be used, and the alloy concentration can be changed according to the application, the degree of shape memory, and the like. Ni
Ni- having a concentration of 49 to 58 atomic%, preferably 50 to 51 atomic%, more preferably 50.3 to 50.7 atomic%.
Ti alloys are preferred.

The shape memory alloy tube constituting the catheter body of the present invention is obtained by subjecting a shape memory alloy tube having a predetermined thickness to ordinary cold working (for example, a cold working rate of 30 to 50%).
It can be formed by stretching according to a conventional method. Thereafter, in the case of the type of shape memory alloy or Ni-Ti alloy, it differs depending on the Ni concentration and cannot be uniquely determined. Is preferably performed.

In the present invention, in order to leave the shape memory property of the shape memory alloy (at least the tip side) and lose superelasticity or pseudoelasticity to obtain a shape memory alloy, nitrogen gas,
Heat treatment is performed in an inert atmosphere such as argon gas. In this case, the heat treatment condition varies depending on the type of the shape memory alloy and the like, and is appropriately selected. For example, in the case of a Ni—Ti alloy, the heat treatment condition is 350 ° C. or more in an inert atmosphere such as an argon gas, although it depends on the Ni concentration. For 1 minute to 100 hours, preferably at 400 ° C. or higher for 10 minutes to 50 hours, more preferably for 4 minutes.
A method of heating at 50 ° C. or higher for 1 to 30 hours can be employed. In some cases, a method of heating at 500 ° C. or more for 10 hours or more in an inert atmosphere such as an argon gas may be employed.

Further, in the catheter of the present invention, it is preferable that the distal end portion (at least about 30 cm, preferably about 50 cm from the distal end) of the shape memory metal portion of the catheter body is tapered as shown in FIG. . The conditions for the taper processing are as follows: the proximal end thickness t ₁ of the catheter body _1.
Is 20 to 200 μm, preferably 30 to 100 μm, while the thickness t ₂ of the distal end of the catheter body 1 is 5 μm.
１００100 μm, preferably 10-50 μm, more preferably 20-40 μm. If the thickness of the tip is less than 5 μm, the tip is too thin and the tip may be broken vertically,
If it exceeds 100 μm, the effect of tapering the tip may not be exhibited. In this case, 1 / 5-4 / 5 of the base end portion thickness t ₁ of the thickness t ₂ of the tip, preferably 1 /
4-3 / 4, more preferably 1 / 3-2 / 3 and t ₂ with respect to the well, for example, t ₁ 50 [mu] m to 25~30μm
It can be.

By tapering the distal end portion of the catheter body in this manner, the distal end portion can be made more flexible, and even if it is in a complicated and meandering fragile blood vessel or the like, it can be damaged. The catheter can be smoothly introduced to the target site without any problems.

That is, in order not to damage the inside of the blood vessel and the like, it is preferable that the introduction distal end portion of the catheter has higher flexibility than other portions. The distal end is tapered to give flexibility toward the distal end, eliminating superelasticity or pseudoelasticity. In order not to return to the original shape immediately and damage to the inside of the blood vessel or the like does not occur, it is preferable that the shape is maintained until the excessive force disappears, and that no repulsive force is generated.

From this point, as described above, the above-mentioned tapered portion allows the catheter body to be heated at 350 to 400 ° C. for 1 to 30 minutes.
Heat treatment at 350 ° C. or more for 1 minute to 100 hours, preferably 40 minutes, in an inert atmosphere such as argon gas.
10 minutes to 50 hours at 0 ° C. or higher, more preferably 450 ° C.
As described above, it is preferable to perform the heat treatment for 1 to 30 hours so as to more reliably exert the flexibility. As a result, the device has sufficient shape memory to return to the original shape at the temperature of the living body, and if an excessive force is applied, even if the tip is bent or bent, the shape gradually (gradually) returns to the original shape. It is formed as follows.

The catheter of the present invention, as described above,
A catheter body, an outer polymer layer covering an outer peripheral surface of the catheter body, a thermoplastic resin tube connected to a distal end of the catheter body, and at least a proximal end of the thermoplastic resin tube from a distal end side of the catheter body. The part side, especially the connecting part between the catheter body and the thermoplastic resin tube and the vicinity thereof is wound in a coil shape or knitted in a mesh shape with a linear elastic material selected from a metal wire, an organic wire and an inorganic wire, or has a linear elasticity. The material is attached along the axial direction or a combination thereof is used to form a reinforcing portion.

In this case, the method of connecting the thermoplastic resin tube to the catheter body includes (a) a method of directly bonding the thermoplastic resin tube to the distal end of the catheter body;
(B) A method of connecting a thermoplastic resin tube via an inner polymer layer formed on the inner peripheral surface of the catheter body.

In the connection method (a), the distal end of the catheter body is connected to the proximal end of the thermoplastic resin tube by bonding, and the distal end side of the catheter main body is connected to at least the proximal end side of the thermoplastic resin tube, in particular. Whether the connection part and its vicinity are wound in a coil shape or knitted in a mesh shape with a linear elastic material selected from a metal wire, an organic wire, and an inorganic wire, or the linear elastic material is stuck along the axial direction of the catheter body. Alternatively, a reinforcing portion is formed by combining these.

In the connection method (b), an inner polymer tube is inserted into the catheter body to form an inner polymer layer on the inner peripheral surface of the catheter body, and the distal end of the catheter body is formed via the inner polymer layer. The thermoplastic resin tube is connected to at least the base end side of the thermoplastic resin tube from the distal end side of the catheter body, particularly the connecting portion and the vicinity thereof are made of a linear elastic material selected from a metal wire, an organic wire and an inorganic wire. The reinforcing portion is formed by winding in a coil shape, knitting in a mesh shape, pasting a linear elastic material along the axial direction of the inner polymer tube, or combining them.

In the connection methods (a) and (b), not only the connecting portion between the cartel body and the thermoplastic resin tube and the vicinity thereof, but also a metal wire from the connecting portion to the tip of the thermoplastic resin tube. It is possible to form a reinforcing portion by winding a coil or knitting a mesh with a linear elastic material selected from an organic wire and an inorganic wire, pasting the linear elastic material along an axial direction, or combining them. preferable. Further, the catheter body is similarly wound from the proximal end to the distal end with a linear elastic material selected from a metal wire, an organic wire and an inorganic wire, or knitted in a mesh shape, or the linear elastic material is applied in the axial direction. It can also be reinforced along with or in combination with them.

In the connection method (a), since the thermoplastic resin tube is directly connected to the distal end of the catheter without the mediation of the inner polymer layer, the inner peripheral surface of the catheter body only needs to be polished. The surface is simply coated with a thermoplastic resin polymer such as a polyurethane-based, nylon-based, or polyolefin-based polymer to form an inner polymer layer, which is excellent in productivity. In this case, the inner polymer layer can be formed on the inner peripheral surface from the catheter body to the tip of the thermoplastic resin tube. The inner polymer layer (the innermost layer) is preferably coated with an antithrombotic hydrophilic polymer.

The method of forming the reinforcing portion is as follows. From the distal end side of the catheter main body to at least the base end side of the thermoplastic resin tube, in particular, the connecting portion between the catheter main body and the thermoplastic resin tube and the vicinity thereof, A wire, a wire elastic material selected from an organic wire and an inorganic wire, wound in a coil shape or knitted in a mesh shape, or a linear elastic material is stuck in the axial direction or a combination thereof to form a reinforcing portion A method, or winding or knitting in a coil shape or a mesh shape with a linear elastic material selected from a metal wire, an organic wire and an inorganic wire from the inside, or attaching the linear elastic material along the axial direction, or a combination thereof There is a method of forming the reinforcing portion by using

As the above method, for example, FIG.
To (C) to 10 (A) to (D). In this case, the catheter body may be coated with an adhesive polymer to improve the adhesion.

Specifically, as shown in FIG.
The distal end of the tubular catheter body 1 and the proximal end of the thermoplastic resin tube 4 are bonded. Next, the connecting portion between the thermoplastic resin tube and the catheter body and its vicinity 5 are wound in a coil shape with a linear elastic material 6 selected from a metal wire, an organic wire and an inorganic wire to form a reinforcing portion 7 (FIG. 8). (B)). In this state, by forming the outer polymer layer 8 on the outer peripheral surfaces of the catheter body 1 and the thermoplastic resin tube 4,
The catheter K is obtained (see FIG. 8C). An inner polymer layer 2 is formed by applying a thermoplastic resin such as polyurethane, nylon, or polyolefin to the inner peripheral surface of the thermoplastic resin tube from the catheter body.

Further, as shown in FIG. 9A, the inner polymer tube 3 is inserted into the tubular catheter body 1 so that the inner polymer tube 3 projects from the tip of the catheter body 1. The inner polymer layer 2 is formed on the inner peripheral surface of the substrate. The thermoplastic resin tube 4 is inserted into the protrusion 3a of the inner polymer tube, and the base end of the thermoplastic resin tube and the distal end of the catheter main body are bonded (see FIG. 9B). Next, a reinforcing portion 7 is formed by winding the connecting portion between the thermoplastic resin tube and the catheter body and its vicinity 5 in a coil shape with a linear elastic material 6 selected from a metal wire, an organic wire, an inorganic wire, and the like (FIG. 9 (C)). In this state,
By forming the outer polymer layer 8 on the outer peripheral surfaces of the catheter body 1 and the thermoplastic resin tube 4, the catheter K is obtained (see FIG. 9D).

As shown in FIGS. 10A to 10D, when the distal end portion 1a of the catheter body is formed in a tapered shape as shown in FIG. The base end portion 4a of the plastic resin tube 4 is also formed in a tapered shape, and these tapered connecting portions and the vicinity 5 are reinforced by being wound in a coil shape with a linear elastic material 6 selected from a metal wire, an organic wire and an inorganic wire. Form the part 7 (FIG. 10)
(C)). In this state, the catheter K is obtained by coating the outer peripheral surface of the catheter body 1 and the thermoplastic resin tube 4 with the outer polymer layer 8 (FIG. 10).
(D)). According to the method shown in FIG. 10, there is no swelling in the connecting portion and the vicinity thereof, which is advantageous in that the diameter of the catheter can be made uniform and small.

On the other hand, as the above method, FIG.
As shown in (A) to (D), a linear elastic material 6 selected from a metal wire, an organic wire, and an inorganic wire is previously coiled at a connection portion of the catheter body of the inner polymer tube 3 and at a position corresponding to the vicinity thereof. To form a reinforcing portion 7 (FIG. 11).
(A)). The inner polymer tube 3 is inserted into the tubular catheter body 1 so that about half of the reinforcing portion 7 projects, and the inner polymer layer 2 is formed on the inner peripheral surface of the catheter body 1.
Is formed (see FIG. 11B). The thermoplastic resin tube 4 is inserted into the protruding portion 3a, and the thermoplastic resin tube base end 4a and the catheter main body distal end 1a are bonded (see FIG. 11C). In this state, the catheter K is obtained by coating the outer peripheral surface of the catheter body and the thermoplastic resin tube with the outer polymer layer 8 (FIG. 1).
1 (D)). In addition, also in the case of this method, it is preferable that the distal end portion of the catheter body and the proximal end portion of the thermoplastic resin tube are formed in a tapered shape.

Although not shown in the drawings, by combining the above methods, it is possible to form a reinforcing portion both at the connecting portion between the catheter body and the thermoplastic resin tube and at both the outside and inside near the connecting portion. Can also. Further, in the above example, the case where the reinforcing portion is wound in a coil shape is shown, but the reinforcing portion may be knitted in a mesh shape, or a linear elastic material may be stuck along the axial direction, or a combination thereof to form the reinforcing portion. It is of course possible to form them.

In this case, by attaching the linear elastic material along the axial direction of the catheter body or the inner polymer tube, the connecting portion between the catheter body and the thermoplastic resin tube and the vicinity thereof are reinforced, and the catheter is elongated. It can be prevented from extending in the vertical direction, and the operability is further improved. The method of attaching the linear elastic material along the axial direction of the catheter body or the inner polymer tube is not particularly limited, and a method of attaching with a glue,
A method of heat welding, a method of embedding in the inner polymer layer or the outer polymer layer, or the like can be appropriately adopted. In this case, the linear elastic material is the catheter body (inner polymer tube)
1 to 10 (especially 2) evenly (symmetrically) along the axial direction of
It is preferable to attach up to six.

As the linear elastic material selected from the metal wire, organic wire and inorganic wire forming the reinforcing portion, metal wires such as platinum coil, stainless steel coil, tungsten coil, polystyrene type, polyolefin type, polyester type, polyurethane Linear thermoplastic elastomers such as nylon 6, aromatic polyester (trade name: Vectran, manufactured by Kuraray Co., Ltd.), aramid (trade name: Kevlar, manufactured by Dupont), etc. Those formed are preferred. In addition, fibrous proteins such as collagen extracted from bovine tendons, etc., carbon fiber,
Glass fibers and other inorganic wires can be used.

The length of the reinforcing portion 7 is not particularly limited as long as the connecting portion between the catheter body and the thermoplastic resin tube and the vicinity thereof can be wound (knitted or attached) without excess or shortage, but more preferably. Not only the connecting part and the vicinity thereof, but also the part from the connecting part to the tip of the thermoplastic resin tube is wound in a coil shape or knitted in a mesh shape with a linear elastic material selected from a metal wire, an organic wire and an inorganic wire, or linearly. It is preferable to reinforce the elastic material by attaching it along the axial direction or by combining them. In addition,
From the base end of the catheter body to the connecting part, and further from the thermoplastic resin tube tip to a metal wire, a wire elastic material selected from an organic wire and an inorganic wire, coiled or knitted into a mesh or knitted or linear The elastic material may be reinforced along the axial direction or a combination thereof.

The thermoplastic resin constituting the above-mentioned thermoplastic resin tube is not particularly limited, and olefin polymers such as polyethylene, polypropylene, polyolefin copolymer, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyurethane, polyamide, Examples include fluororesins such as polyester and polytetrafluoroethylene, polymers such as cellulose, polycarbonate, silicone, natural rubber latex, and other rubbers that can withstand radiation electron sterilization such as electron beam and γ-ray. In this case, the length of the thermoplastic resin tube is not particularly limited, but 1 mm to 200 cm, preferably 1 mm
To 50 cm, more preferably about 1 mm to 30 cm.

As described above, the connecting portion between the thermoplastic resin tube and the distal end of the catheter body and the vicinity thereof are wound in a coil shape or knitted in a mesh shape with a linear elastic material selected from a metal wire, an organic wire and an inorganic wire. By sticking the linear elastic material along the axial direction or forming a reinforcing part by combining these, excellent flexibility is particularly given to the catheter tip part, and a minute blood vessel that makes the catheter complicated and meandering, Even a ureter, a pancreatic bile duct, or the like can smoothly lead, does not bend, and can prevent discomfort and pain as much as possible.

Further, in the catheter of the present invention, a metal layer containing no Ni (inner metal layer) between at least the inner peripheral surface of the shape memory metal portion and the inner polymer layer of the catheter main body, and the outer peripheral surface of the catheter main body It is also possible to form a metal layer (outer metal layer) between the metal layer and the outer polymer layer.

FIG. 12 is a sectional view of the distal end showing one embodiment of such a catheter K. Although not shown, a thermoplastic resin tube is connected to the distal end of the catheter K. The distal end of the catheter K covers the outer peripheral surface of the catheter main body 1 made of the shape memory metal 1a to form the outer polymer layer 8, and the inner side of the inner peripheral surface of the catheter main body 1 with the inner polymer layer 2. The inner metal layer 9 containing no Ni is formed. Although not shown, an outer metal layer may be formed between the outer peripheral surface of the catheter body 1 and the outer polymer layer 8. On the outer polymer layer 8 (outermost layer) and on the inner polymer layer 2 (innermost layer), the operability is increased, and the surface is highly durable and has good antithrombotic properties, lubricity in water and sliminess. , A hydrophilic polymer such as a polyurethane-based, nylon-based, or polyolefin-based polymer.

As the resin constituting the inner polymer layer 2 and the outer polymer layer 8, the same thermoplastic resin as the thermoplastic resin tube can be used.

As the inner metal layer 9 made of a metal not containing Ni, a metal having high conductivity is preferably used. For example, copper, silver, gold, platinum, palladium, tungsten, tantalum, iridium, A metal selected from alloys of the above can be used. The outer metal layer formed between the outer peripheral surface of the catheter body 1 and the outer polymer layer 8 may contain Ni, and can be formed from the same material as the inner metal layer 9.

By forming a polymer layer or an inner metal layer containing no Ni over the inner surface of the shape memory metal portion as described above, when the shape memory metal portion is a Ni—Ti alloy, To prevent the release of Ni ions.

In this case, the thickness of the catheter body 1 can be about 5 to 300 μm, particularly about 10 to 200 μm, and the thickness of the outer polymer layer 8 is 1 to 300 μm, preferably 20 to 300 μm, particularly 50 to 150 μm. can do. The thickness of the inner polymer layer 2 is 10 to 100 μm when the inner polymer layer is formed by inserting the inner polymer tube, and the inner polymer layer is formed by applying a thermoplastic resin polymer to the inner peripheral surface of the catheter body. When it is formed, it can be about 0.2 to 30 μm. The thickness of the inner metal layer 9 can be 0.2 to 20 μm, and the thickness of the outer metal layer can be 0.2 to 20 μm. As described above, the inner diameter of the catheter K in which the polymer layer or the metal layer is formed on the inner and outer peripheral surfaces of the catheter body 1 can be appropriately selected, but is 50 to 5000 μm, particularly 100 to 100 μm.
It can be formed to a small diameter of 0 μm.

A thermoplastic resin tube of the catheter,
The thermoplastic resin forming the inner polymer layer and the outer polymer layer may contain an X-ray contrast agent. In this case, a known X-ray contrast agent can be used, but in the present invention, tungsten powder is preferable. Further, the content of the X-ray contrast agent can be about 20 to 69% by weight.

The method of manufacturing a catheter in which a metal layer is formed on the inner and outer peripheral surfaces of the catheter body is as follows. Electroplating or electroless plating, particularly non-electrolytic plating, is performed on the inner and outer peripheral surfaces of a shape memory alloy tube having a predetermined thickness. It can be formed by forming a metal film by an appropriate method such as electrolytic plating, and then stretching it according to a conventional method.

The length of the catheter K can be appropriately selected according to the intended use.

Further, the catheter can be stored in a shape memory so that the distal end of the catheter is curved within a range of a radius of curvature (R) of about 0 to 200 mm at a living body temperature.
Shape memory can be made to bend at 0 °, especially 30-90 °. Note that the radius of curvature (R) of 0 mm indicates a straight state without being curved, which is necessary depending on the purpose of use. By storing the shape of the catheter in this way, it is possible to smoothly and more easily guide the catheter into a steep blood vessel or the like.

[0100] The catheter of the present invention can eliminate the need for a guide wire for guidance by providing strength (rigidity) to the proximal end side. In addition, since it can be formed extremely thin and at least the distal end portion of the catheter body eliminates the superelastic effect or the pseudoelastic effect at least at the temperature of the living body, when a certain stress is applied to the catheter in a blood vessel or the like, it is easily collapsed. Although it does not bend and does not damage the blood vessel wall etc. due to the small force to return to its original shape, it has a sufficient shape memory effect, so it can be gradually restored to its original shape. Thus, operability and safety have been dramatically improved as compared with the related art.

The catheter can be used for examination of angiography of the brain, heart, abdomen, etc., treatment of stenosis of the blood vessels of the brain, heart, abdomen, etc., treatment of calculi of urinary system such as ureter, urethra, and pancreatic biliary tract. It can be used in the same manner as an ordinary catheter for inspection of ERCP, treatment of ERCP, foreign substance removal and recovery, and the like. Specifically, the tip of the catheter is inserted to a target site in a living body by a normal method, and various agents such as an angiographic agent and an embolic substance are locally injected, and the tip is expanded and contracted. By attaching a possible balloon, it can be used for treating various blood vessels, ureters, and pancreaticobiliary ducts.

Further, by forming a metal layer having excellent conductivity on the inner peripheral surface or the inner peripheral surface and the outer peripheral surface of the catheter body, not only protection of the inner and outer peripheral surfaces but also melting and cutting of the thermoplastic resin tube can be performed. For detachment of the connection member of the medical wire having the indwelling member, the in vivo indwelling member is further replaced with PVA, E
When they are bound by VA or the like, they can be used also when releasing this connecting polymer.

In this case, the in-vivo indwelling member is introduced into the catheter lumen in which the inner peripheral surface of the catheter is formed of a metal not containing Ni, and the in-vivo indwelling member is connected to a connecting member (such as PVA).
After passing through the position, by flowing a monopolar high-frequency current from the inner metal layer of the catheter to melt and cut the thermoplastic resin tube, various in-vivo indwelling members can be easily and reliably cut and indwelled. Things.

Further, for patients who cannot use high-frequency current, an outer metal layer is also formed on the outer peripheral surface of the catheter body, so that the inner metal layer on the inner peripheral surface of the catheter body and the outer metal layer on the outer peripheral surface of the catheter body can be formed. The thermoplastic resin tube can be configured to be melt-cuttable by supplying a bipolar high-frequency current using the metal layer. Further, the catheter of the present invention can be applied to brain wave measurement.

In the catheter of the present invention, the innermost and outer peripheral surfaces of which are coated with the above-mentioned hydrophilic polymer have excellent antithrombotic properties and surface slipperiness, and have all operability required in the field. It is. Further, the catheter of the present invention can be widely applied from a certain diameter to a very small diameter,
Even small, meandering blood vessels and ureters such as the heart, brain, abdomen, and urinary tract can be inserted smoothly and reliably into the target site without causing vascular or ureteral damage. .

Although the catheter of the present invention is not particularly limited, a ureteral catheter for crushing and removing ureteral stones and the like, a catheter used for a retriever member for removing and collecting foreign matter, an endoscope Catheters (catheters used for endoscopy), examination of angiography of brain, heart, abdomen, etc., embolization treatment of brain, heart, abdomen, etc., endovascular surgery of brain, heart, abdomen, etc. It is suitable for catheters for endoscopic retrograde pancreatobiliary contrast (ERCP) and for treatment.

Next, the catheter for removing and collecting foreign matters and the calculus capturing device of the present invention has an operation member having a foreign matter removing and collecting means and a calculus capturing means at its distal end inserted through the lumen thereof. At least the distal end side of the member has shape memory at least at a biological temperature, and is formed of a shape memory metal having no superelasticity or pseudoelasticity, particularly when the operating member is deformed at the biological temperature, It takes 0.3 seconds or more, preferably 0.5 seconds or more, more preferably 1 second or more, still more preferably 1.5 seconds or more, and most preferably 2 seconds or more to restore.

More specifically, the preferred ranges of the yield load, the recovery load, and the residual strain in the three-point bending test of the operating member differ depending on the outer diameter of the operating member, and are preferably the following ranges. When the operation member is composed of a plurality of wires, a bundle of these satisfies the following conditions.

<When the outside diameter of the operation member is 600 to 800 μm> (i) The yield load is 9.8 N or less, preferably 6.4 N or less, more preferably 5.4 N or less, and further preferably 4.
It is preferably at most 4N, most preferably at most 2.9N. (Ii) The recovery load is 3.9N or less, preferably 2.9N
Or less, more preferably 1N or less, still more preferably 0.5N or less.
It is preferably N or less. (Iii) The residual strain is 0.2 mm or more, preferably 0.1 mm or more.
It is preferably at least 5 mm, more preferably at least 0.9 mm, even more preferably at least 1.2 mm.

<The outer diameter of the operation member is 300 μm or more and 600
When it is less than μm> (i) The yield load is 7.8 N or less, preferably 4.9 N or less, more preferably 3.9 N or less, and still more preferably 2.
It is preferably 9 N or less, most preferably 2 N or less. (Ii) The recovery load is 2.9N or less, preferably 1N or less, more preferably 0.5N or less, and still more preferably 0.5N or less.
It is preferably 1 N or less. (Iii) The residual strain is 0.2 mm or more, preferably 0.1 mm or more.
It is preferably at least 5 mm, more preferably at least 0.9 mm, even more preferably at least 1.2 mm.

<When the outside diameter of the operation member is less than 300 μm> The yield load is 2 N or less, more preferably 0 to 1 N,
It is preferable that the recovery load is 2 N or less, more preferably 0 to 1 N, and the residual strain is 0.1 mm or more, more preferably 0.9 mm or more.

The foreign matter removing / recovering means and the calculus capturing means are not particularly limited. For example, a shape memory alloy such as a Ni--Ti alloy is used to perform plastic deformation below the transformation point temperature and to heat above the transformation point temperature. It is preferable to use a capturing means formed so as to return to a shape enclosing a calculus or a foreign substance when the capturing is performed.

More specifically, the capturing means 41 made of a shape memory alloy shown in FIGS. 13A and 13B heats the tips of four operation wires 40 (only two are shown in the figure). Is stored in a spiral shape. Using a catheter K in which an operation wire having this capturing means 41 at the tip is inserted, when the tip reaches a calculus or foreign matter portion, the operation wire 40 is pushed out, and the calculus or foreign matter 4 is removed.
The capture means 41 is extended to the rear of 2. By energizing or heating the wire 40 in this state, the capture means 41 is deformed in a spiral shape to capture the calculus or foreign matter 42. The shape of the capture means at the time of the return deformation is not particularly limited as long as it can capture stones or foreign substances, and can be various shapes such as a key shape and a spiral shape. The number of operation wires can be two or more, preferably two to ten.

14A to 14C, the capture means 41 made of a shape memory alloy is housed in a state where the capture means 41 made of a shape memory alloy is contracted in the catheter K up to a calculus or a foreign substance. When the operation wire 40 is pushed out at the stage where the foreign matter portion is reached, the capture means 41 is spontaneously expanded by the action of the leaf spring, and the calculus or the foreign matter 42 is wrapped. By energizing or heating the wire 40 in this state, the capturing portion can be narrowed and the calculus or the foreign matter 42 can be captured.

Further, the capture means shown in FIG.
The trapping means 41 is composed of four wires whose shape is stored in a constricted shape so that a calculus or a foreign substance can be wrapped in advance. This capturing means is shown in FIG.
As shown in (B) to (E), the capturing means 41 is housed in the catheter K until reaching the calculus or foreign matter portion. By extruding, the catching means spontaneously spreads and wraps the calculus or foreign matter 42 so as to sew it, thereby capturing the calculus or foreign matter 42.

FIG. 16 shows a capture means 41 comprising a pair of concave and openable arms. The capture means 41 is for capturing the calculus or foreign matter by pulling the two shafts 43 extending from the operating member 40 at the calculus or foreign matter site. The shape of the concave arm is not particularly limited, and it may be formed in a pair of bowl shapes (cup shapes) or the like.

FIG. 17 shows an example in which a trapping means 41 formed in a cage-like shape by four elastic wires is used as the trapping means. By extruding the operation wire 40 at the target portion, the capturing means 41 expands in a basket shape, and can capture calculus or foreign matter therein. The number of elastic wires is 4 to 10
It is a book.

As described above, in the catheter for removing and collecting foreign matter and the calculus capturing device according to the present invention, at least the distal end side of the catheter body and the operating member having the foreign matter removing and collecting means and the calculus capturing means at least have a shape memory at biological temperature. Since it is formed of a shape-memory metal having no superelasticity or pseudoelasticity, even a complicated and meandering minute blood vessel or ureter, which is difficult with a conventional catheter, Without damaging blood vessels, ureters, etc.
The foreign matter removal and collection means and stone capture means can be smoothly transported to the target site, the performance of the foreign matter removal and collection means and stone capture means can be fully exploited, and high foreign matter removal and collection performance and stone capture performance can be improved You can do it.

The catheter of the present invention can be used not only to capture stones formed in the kidney, ureter, abdomen, liver, gall and pancreatic duct system, but also to prevent lumps of emboli, broken wires and broken articles such as tubes and the like. It can be widely used as a retriever catheter for removing and collecting foreign substances such as foreign substances and blood clots, and can achieve good results of removing and recovering foreign substances and capturing stones.

[0120]

EXAMPLES The present invention will be described below in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Example 1, Comparative Example 1] Ni was 49 to 58.
The cylindrical body made of an atomic% Ni—Ti alloy is cold-worked and stretched according to a conventional method to obtain an outer diameter of 875 μm and an inner diameter of 7 mm.
A catheter body having a thickness of 50 μm and a thickness of about 63 μm was prepared. This catheter body was heat-treated at 400 ° C. for 10 to 30 minutes.

Next, 30 cm from the tip of the catheter body
Up to 450 ° C in argon gas
Heat-treat for 10 hours, and further from the tip of the catheter body
Up to 2.5 cm at 400 ° C in argon gas
Heat treatment was performed for 4 hours. Thereby, the proximal end side of the catheter main body has relatively rigidity and flexibility, while the distal end side of the catheter main body has flexibility toward the distal end and has shape memory at biological temperature,
A catheter body made of a shape memory alloy having no superelasticity or pseudoelasticity was obtained (Example 1).

For comparison, a cylindrical body made of an Ni—Ti alloy containing 49 to 58 atomic% of Ni was cold-worked and stretched according to a conventional method to obtain an outer diameter of 875 μm and an inner diameter of 750 μm.
m, a catheter body having a thickness of about 63 μm was prepared. A catheter body made of a shape memory alloy (having shape memory properties and superelasticity or pseudoelasticity) which was merely heat-treated at 400 ° C. for 10 to 30 minutes was produced (Comparative Example 1).

As shown in FIG. 1, with respect to the obtained catheter bodies of Example 1 and Comparative Example 1, a portion of the catheter body up to 15 cm from the tip of the catheter body was supported on a rubber plate and deformed at an angle α = 90 degrees. When the deformation force is released, the first embodiment
The catheter body slowly recovered (gradually) in about 2 seconds at a biological temperature (33-42 ° C., preferably 35-38 ° C.). In contrast, the catheter body of Comparative Example 1 was instantaneously restored in less than 0.3 seconds.

Further, the yield load,
The recovery load and residual strain were measured. Table 1 shows the results. Three-point bending test As shown in FIG.
And 1 mm for each measurement site under the following measurement conditions
The yield load and the recovery load at the time of displacement were measured, and the residual strain was determined from the residual displacement after release of the load. <Measurement conditions> Test speed: 2 mm / min Punch tip shape: φ5 mm Support point shape (ad): φ6 mm Distance between support points (ab): 18 mm Distance between support points (cd): 14 mm Punch displacement: 2 mm Measurement Temperature: 37 ± 1 ℃

[0126]

[Table 1]

Next, as shown in FIGS. 8 (A) to 8 (C), a thermoplastic resin tube having a length of about 10 cm was connected to the distal end of the obtained catheter body of Example 1 and Comparative Example 1. Then, a reinforcing portion was formed by winding a metal wire in a coil shape from the outside around the connecting portion between the thermoplastic resin tube and the catheter body and in the vicinity thereof. Next, an inner polymer layer and an outer polymer layer were formed of a thermoplastic resin on the inner and outer peripheral surfaces of the catheter body and the thermoplastic resin tube, respectively, and the catheters of Example 1 and Comparative Example 1 were produced.

The catheter of Example 1 has a radius (R) of about 1 mm (arteriole) to about 50 mm (aortic arch, etc.) at the distal end of the catheter in order to increase the rigidity (torque property) of the proximal end. 0-120 degrees, especially 30-90
The shape was memorized in the range of degrees.

The obtained catheter of Example 1 had a flexible catheter body and high flexibility. In addition, since the distal end portion 1 to 50 mm is formed at an angle so that the catheter can be inserted smoothly after the catheter enters the target blood vessel, there is no damage to the blood vessel. Further, the distal end side of the catheter body has no superelasticity or pseudoelasticity, and from this point, damage in the blood vessel can be suppressed as much as possible. Note that the distal end side of the catheter body has a shape memory effect of gradually (gradually) recovering at the temperature of the living body even if bending or bending occurs. The proximal end of the catheter has sufficient rigidity and can be operated without a guide wire.

On the other hand, the catheter of Comparative Example 1
In particular, since the distal end side has superelasticity or pseudoelasticity, the rigidity is high, and it is difficult to insert it into a meandering fine blood vessel or the like, and if it is forcibly inserted, the blood vessel or the like may be damaged. In addition, due to the difference in flexibility between the leading thermoplastic resin tube and the catheter main body, a step is generated at the connecting portion between the thermoplastic tube and the catheter main body, resulting in poor operability and safety.

Example 2 N is 49 to 58 atomic% of N
The i-Ti alloy cylinder is cold-worked and stretched according to a conventional method, so that an outer diameter of 725 μm, an inner diameter of 625 μm,
A catheter body having a thickness of 50 μm was prepared. This catheter body was heat-treated at 400 ° C. for 10 to 30 minutes. Next, the distal end side of the catheter main body up to 30 cm from the distal end was heat-treated at 400 ° C. for 24 hours in argon gas.

With respect to the catheter body after the treatment, the portion from the tip to 15 cm was deformed to an angle α = 90 degrees by the method shown in FIG. 1 and the deforming force was released. (Slowly) restored. Also,
The same three-point bending test as described above was performed. Table 2 shows the results.

Example 3 N is 49 to 58 atomic% of N
The i-Ti alloy cylinder is cold-worked and stretched according to a conventional method to obtain an outer diameter of 600 μm, an inner diameter of 500 μm,
A catheter body having a thickness of 50 μm was prepared. This catheter body was heat-treated at 400 ° C. for 10 to 30 minutes. Next, the distal end side of the catheter main body up to 30 cm from the distal end was heat-treated at 400 ° C. for 24 hours in argon gas.

In the catheter body after the treatment, the portion from the distal end to 15 cm was deformed to an angle α = 90 degrees by the method shown in FIG. 1 and the deforming force was released. (Slowly) restored. The same three-point bending test was performed as described above. Table 2 shows the results.

Example 4 N is 49 to 58 atomic% of N
The i-Ti alloy cylinder is cold-worked and stretched according to a conventional method to obtain an outer diameter of 320 μm, an inner diameter of 220 μm,
A catheter body having a thickness of 50 μm was prepared. This catheter body was heat-treated at 400 ° C. for 10 to 30 minutes. Next, the distal end side of the catheter main body up to 30 cm from the distal end was heat-treated at 400 ° C. for 24 hours in argon gas.

With respect to the catheter body after the treatment, the portion from the tip to 15 cm was deformed to an angle α = 90 degrees by the method shown in FIG. 1 and the deforming force was released. (Slowly) restored. A three-point bending test was performed in the same manner as in Example 1 above. Table 2 shows the results.

[0137]

[Table 2]

As shown in FIGS. 8 (A) to 8 (C), about 5 to 1
A thermoplastic resin tube having a length of 0 cm was connected, and a reinforcing portion was formed by winding a metal wire from outside on a connecting portion between the thermoplastic resin tube and the catheter body and in the vicinity of the connecting portion. Next, an inner polymer layer and an outer polymer layer were formed of a thermoplastic resin on the inner and outer peripheral surfaces of the catheter body and the thermoplastic resin tube, whereby catheters of Examples 2 to 4 were produced.

The obtained catheters of Examples 2 to 4 have a flexible and flexible catheter body, and have no step at the connecting portion between the leading thermoplastic resin tube and the catheter body and in the vicinity thereof. The catheter can be smoothly introduced into blood vessels and the like, and is excellent in operability and safety.

[0140]

According to the present invention, there is no step at the connecting portion between the leading thermoplastic resin tube and the catheter body, and the occurrence of uncomfortable feeling and pain is extremely small, and the inside of the blood vessel or ureter can be damaged during operation. It can be prevented as much as possible.

The catheter of the present invention eliminates the superelastic effect or the pseudoelastic effect while leaving the shape memory effect at least on the distal end side of the catheter body.
By forming the proximal end side of the catheter body so as to have rigidity, it has excellent flexibility, flexibility and sufficient stiffness, can be operated without a guide wire for guidance, and is excellent in safety and operability It is.

Further, in the catheter for removing and collecting foreign matter and the calculus capturing device of the present invention, the catheter body and the operating member having the foreign matter removing and collecting means and the calculus capturing means at the tip are both formed of a shape memory alloy. Even in the case of a complicated and meandering minute blood vessel or ureter, which has been difficult with a conventional catheter, the foreign matter removing and collecting means and the calculus capturing means can be smoothly moved to the target site without damaging the inside of the blood vessel or the ureter. It can be transported, and can achieve safe and high foreign matter removal / recovery performance and stone capture performance.

[Brief description of the drawings]

FIGS. 1A to 1C are explanatory views showing a bending test method.

FIG. 2 is an explanatory view showing a measuring method of a three-point bending test.

FIG. 3 is an explanatory diagram showing the measurement site.

FIG. 4 is a graph showing a relationship between a yield load and a recovery load.

FIG. 5 is a graph showing the relationship between yield load and residual strain.

FIG. 6 is a conceptual diagram showing a relationship among a yield load, a recovery load, and residual strain.

FIG. 7 is a partial cross-sectional view showing a state where a distal end portion of the catheter body is tapered.

FIG. 8 is a partial cross-sectional view showing a method of connecting a thermoplastic resin tube to the distal end of a catheter body and forming a reinforcing portion according to the present invention.

FIG. 9 is a partial cross-sectional view showing a method of connecting a thermoplastic resin tube to the tip of another catheter body and forming a reinforcing portion.

FIG. 10 is a partial cross-sectional view showing a case where a distal end portion of the catheter body and a proximal end portion of a thermoplastic resin tube are further tapered.

FIG. 11 is a partial cross-sectional view formed by winding the reinforcing portion from the inside.

FIG. 12 is a partial cross-sectional view of a catheter according to one embodiment of the present invention.

FIG. 13 is an explanatory view showing a state in which calculus and foreign matter are captured using the catheter for removing and collecting foreign matter and capturing stones according to the present invention.

FIG. 14 is an explanatory diagram showing a state of capturing another calculus or foreign matter.

FIG. 15 is an explanatory diagram showing a state of capturing still another calculus or foreign matter.

FIG. 16 is a schematic view showing a calculus and foreign matter capturing means of the present invention.

FIG. 17 is a schematic view showing another means for capturing stones and foreign matter.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Catheter main body (tube) 2 Inner polymer layer 3 Inner polymer tube 4 Thermoplastic resin tube 5 Connecting part and its vicinity 6 Linear elastic material 7 Reinforcement part 8 Outer polymer layer 9 Inner metal layer 40 Operating member 41 Capture means 42 Calculus (Foreign body) K catheter

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Keiya Usami 2-3-4 Minamiyukiya, Ota-ku, Tokyo (72) Inventor Tomino Usami 2-3-4 Minamiyukiya, Minamiyukiya, Ota-ku, Tokyo (72) Inventor Rino Tokyo 2-3-4 Minamiyukiya, Minamiyukiya, Ota-ku, Tokyo (72) Minamino Usami 2-3-4 Minamiyukiya, Minamiyukiya, Tokyo, Japan (72) Keiko Usami 2-3-4 Minamiyukiya, Ota-ku, Tokyo F-term (reference) 4C060 EE22 EE24 4C081 AC08 BB07 BB08 CG03 DA03

Claims (22)

[Claims] At least the distal end side has a catheter body formed of a shape memory metal not having superelasticity or pseudoelasticity and having shape memory at least at a biological temperature, and an outer peripheral surface of the catheter body. An outer polymer layer to be coated, and a thermoplastic resin tube connected to the distal end of the catheter body, and a metal wire, an organic wire and at least a proximal end side of the thermoplastic resin tube from the distal end side of the catheter main body. It is characterized in that a reinforcing portion is formed by winding a coil or knitting a mesh with a linear elastic material selected from inorganic wires, pasting the linear elastic material along the axial direction, or combining them. catheter. 2. The catheter according to claim 1, wherein an inner polymer layer is formed by applying a polymer to inner peripheral surfaces of the catheter body and the thermoplastic resin tube. 3. A metal wire from at least the proximal end side of the thermoplastic resin tube from the distal end side of the catheter main body to the outside,
A coiled or knitted mesh of a linear elastic material selected from organic wires and inorganic wires, or a linear elastic material stuck along the axial direction or a combination of these to form a reinforcing portion 3. A catheter according to claim 1 or claim 2. 4. The distal end of the catheter body and the proximal end of the thermoplastic resin tube are formed in a tapered shape, and the tapered connecting portion and its vicinity are wires selected from the outside from a metal wire, an organic wire and an inorganic wire. 4. The reinforcing portion is formed by winding a coil-shaped or knitting mesh-shaped elastic material, attaching a linear elastic material along an axial direction, or combining them. Catheter. 5. A method of winding or knitting a connecting portion between the catheter body and the thermoplastic resin tube and the vicinity thereof from the inside with a linear elastic material selected from a metal wire, an organic wire and an inorganic wire in a coil shape or a mesh shape. The catheter according to any one of claims 1 to 4, wherein a linear elastic material is attached along an axial direction or a combination thereof is used to form a reinforcing portion. 6. The catheter according to claim 1, wherein the thermoplastic resin tube contains an X-ray contrast agent. 7. The catheter according to claim 1, wherein when at least the distal end side of the catheter body is deformed at the biological temperature, it takes 0.3 seconds or more to recover. 8. At least the distal end side of the catheter body,
Formed of a metal material with a yield load of 8.8 N or less, a recovery load of 2.9 N or less, and a residual strain of 0.2 mm or more when a three-point bending test is performed using a tube having an outer diameter of 875 μm and an inner diameter of 750 μm. The catheter according to any one of claims 1 to 7, further comprising: 9. At least the distal end side of the catheter body,
4. The shape memory alloy which is formed of the shape memory metal and has a shape memory alloy having superelasticity or pseudoelasticity while having a shape memory property at least at a biological temperature. 9. The catheter according to any one of 8 above. 10. The catheter according to claim 1, wherein a tip portion of the shape memory metal portion is formed in a tapered shape. 11. The catheter according to claim 1, wherein a shape of the distal end portion of the shape memory metal portion is stored so as to be curved at a biological temperature within a radius of curvature of 0 to 200 mm. 12. The method according to claim 1, wherein the shape-memory metal portion is set at a biological temperature of 0.
The catheter according to any one of claims 1 to 11, wherein the catheter is shape-memory so as to be bent by 120 °. 13. The Ni-T in which the shape memory metal has lost superelasticity or pseudoelasticity at least at a biological temperature.
The catheter according to any one of claims 1 to 12, wherein the catheter is an i-based, Fe-based, or Cu-based shape memory alloy. 14. The catheter according to claim 2, wherein an inner metal layer containing no Ni is formed between at least the inner peripheral surface of the shape memory metal portion of the catheter body and the inner polymer layer. 15. The catheter according to claim 1, wherein an outer metal layer is formed between at least an outer peripheral surface of the shape memory metal portion of the catheter body and the outer polymer layer. 16. The catheter according to claim 14, wherein a monopolar high-frequency current is applied to the thermoplastic resin tube using an inner or outer metal layer of the catheter body so that the tube can be melt-cut. 17. An inner metal layer containing no Ni is formed between the inner peripheral surface of the catheter body and the inner polymer layer, and an outer metal layer is formed between the outer peripheral surface of the catheter body and the outer polymer layer. Using these inner and outer metal layers, a bipolar high-frequency current is passed through the thermoplastic resin tube,
15. The tube according to claim 2, wherein the tube can be melt-cut.
The catheter according to any one of the preceding claims. 18. At least the distal end side of the catheter main body is formed of a shape memory metal having shape memory at least at a biological temperature and not having superelasticity or pseudoelasticity, and at least the distal end of the catheter main body. When the side was deformed at the living body temperature, it took 0.3 seconds or more to recover, and at least the distal end side of the catheter body was subjected to a three-point bending test using a tube having an outer diameter of 875 μm and an inner diameter of 750 μm. A catheter formed of a metal material having a yield load of 8.8 N or less, a recovery load of 2.9 N or less, and a residual strain of 0.2 mm or more. 19. At least the distal end side of the catheter main body is formed of a shape memory metal that has shape memory at least at a biological temperature and does not have superelasticity or pseudoelasticity, and at least the distal end of the catheter main body. When the side was deformed at the living body temperature, it took 0.3 seconds or more to recover, and at least the distal end side of the catheter body was subjected to a three-point bending test using a tube having an outer diameter of 875 μm and an inner diameter of 750 μm. A catheter made of a metal material having a yield load of 8.8 N or less, a recovery load of 2.9 N or less, and a residual strain of 0.2 mm or more, wherein the catheter body has a metal from the base end to the tip end. Whether it is wound in a coil shape or knitted in a mesh shape with a linear elastic material selected from a wire, an organic wire and an inorganic wire, or the linear elastic material is stuck along the axial direction There is a catheter, characterized in that reinforced in combination. 20. The catheter according to any one of claims 1 to 19, wherein an operation member having a calculus capturing means or a foreign matter removing and collecting means at a distal end thereof is inserted into the catheter lumen. 21. At least a tip side of the operation member,
21. The catheter according to claim 20, wherein the catheter is formed of a shape-memory metal having shape memory at least at a biological temperature and not having superelasticity or pseudoelasticity. 22. The catheter according to claim 21, wherein, when at least the distal end side of the operating member is deformed at the biological temperature, it takes 0.3 seconds or more to recover.