JP2000014764A - Catheter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve insertability, a torque transmitting property, and workability by forming at least a part of a catheter of a metal tube, making at least the tip thereof of copper-based alloy made up of a specific wt.% of Mn, a specific wt.% of Al, the balance of Cu, and unavoidable impurities taking the rest. SOLUTION: At least a part of a catheter 1 is composed of a metal tube. For example, the catheter 1 is formed of a superelastic Cu-Al-Mn alloy pipe, and bending elasticity is decreased gradually from a base portion 2a to an intermediate portion 2b further to a distal end 2c. The distal end 2c is made gradually more flexible toward the tip. Furthermore, at least the distal end 2c is formed of a copper-based alloy comprised of 5 to 20 wt.% Mn, 3 to 10 wt.% Al, and Cu and unavoidable impurities accounting for the rest. This composition gives sufficient rigidity to the base portion 2a and sufficient flexibility to the distal end 2c and ensures safe use.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catheter used by inserting into a tubular organ such as a blood vessel, a digestive tract, a trachea and the like.

[0002]

2. Description of the Related Art Intravascular catheters used for intravascular treatment and treatment include:
There are types such as angiographic catheters, PTCA (coronary coronary angioplasty) catheters, and catheters for angioplasty. In order to introduce a catheter into a blood vessel, a guide wire is first inserted into a treatment site in the blood vessel, and the tip of the intravascular catheter is introduced along the guide wire. When the distal end portion of the catheter is advanced into the blood vessel, the catheter is pushed or twisted (rotated) in order to pass through a narrow and tortuous blood vessel path. Therefore, considerable rigidity is required at the hand of the operator, that is, at the proximal end of the catheter. The tip must have sufficient flexibility so as not to damage the blood vessel wall.

There are many products on the market that take measures to provide the above-mentioned properties to the distal end and the proximal end of the catheter, but they can be mainly classified into the following two types. One is to use a synthetic resin with high rigidity at the base end, and to attach a flexible soft tip tube piece at the end at the time of processing, and the other is to use a metal thin wire knitting called a blade at the base end. This is the method used for the part. However, to maintain a balance between rigidity and flexibility from the base end to the tip,
Furthermore, it is necessary to use a different material for the intermediate portion, and there is a problem that the moldability is very difficult. In addition, the angiography catheter used when injecting a contrast agent into a blood vessel with a syringe or the like must have a blade to the distal end side in order to have pressure resistance when high pressure is applied to the catheter due to the viscosity of the contrast agent. . Therefore, there is a problem that the flexibility on the tip side is slightly lacked.

[0004] For this reason, catheters having a blade made of a super-elastic Ni-Ti alloy capable of giving flexibility to the distal end of the catheter are often used.

[0005] However, the superelastic Ni-Ti alloy is
On the other hand, while showing good flexibility, there is a case where it is difficult to introduce into a desired site in the body because the insertion operation into a blood vessel is not successful due to lack of rigidity. In addition, it is difficult to significantly change the physical properties of the Ni-Ti alloy by heat treatment, and it is not practical to obtain appropriate rigidity and flexibility except for changing the diameter (for example, by tapering). Furthermore, due to poor workability, thinning and subsequent post-processing are difficult, weldability and adhesion are poor, and there is a problem in safety when combined with other materials.

Accordingly, an object of the present invention is to provide flexibility at the distal end portion, maintain appropriate elasticity and rigidity at the base end portion, excel in insertion operability and torque transmission, and excel in workability. It is to provide a catheter.

[0007]

Means for Solving the Problems In view of the above problems, as a result of earnest studies, the present inventors have found that the use of a Cu-Al-Mn base shape memory alloy allows the tip to have appropriate elasticity. With the discovery, Cu-Al-Mn
By utilizing the properties of the tilt function, in which the properties of the base alloy change gradually, the stiffness of the catheter can be gradually changed, and a catheter having extremely excellent insertion operability and torque transmission can be obtained. Thus, the present invention has been completed.

That is, the first catheter of the present invention comprises:
At least a part is composed of a metal tubular body, and at least a tip portion of the metal tubular body has Mn of 5 to 20% by weight.
And a copper-based alloy comprising 3 to 10% by weight of Al, the balance being Cu and unavoidable impurities.

In a second catheter of the present invention, a metal reinforcing material is included in at least a part of a catheter tube, and the metal reinforcing material has a Mn of 5 to 20% by weight.
And a copper-based alloy comprising 3 to 10% by weight of Al, the balance being Cu and unavoidable impurities.

[0010] In the catheter of the present invention, the copper-based alloy may further comprise Ni, Co, Fe, Ti, V, Cr, Si,
Nb, Mo, Sn, Ag, W, Mg, P, Zr, Zn,
One or more selected from the group consisting of B and misch metal can be contained in a total amount of 0.001 to 10% by weight.

[0011] It is preferable that the copper-based alloy has a bending elasticity that decreases continuously or stepwise in a direction from the proximal end to the distal end of the catheter. Such a copper-based alloy is formed by hot working and / or cold working, rapidly cooled after being maintained at a temperature of 500 ° C. or more, and further heated continuously in a direction from the proximal end to the distal end of the catheter. It is obtained by aging at a temperature distribution that gradually or stepwise decreases. The highest temperature of the temperature distribution is 250-350 ° C, and the lowest temperature of the temperature distribution is less than 250 ° C.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [1] Copper-based alloy (1) Composition of copper-based alloy The copper-based alloy used in the present invention is composed of Al 3 to 10% by weight, Mn.
5 to 20% by weight, with the balance being Cu and unavoidable impurities. This copper-based alloy undergoes a β (bcc structure) single phase at a high temperature and a martensite (non-diffusion) transformation at a low temperature. In addition, the structure of this β single phase is subjected to a heat treatment at about 300 ° C., and the α phase (fc
c structure) and a Heusler phase (ordered bcc structure).

When the content of the Al element is less than 3% by weight, a β single phase cannot be formed, and when it exceeds 10% by weight, it becomes extremely brittle. Although the content of the Al element varies depending on the composition of the Mn element, the preferable content of the Al element is 6 to 10% by weight.

By containing the Mn element, the range of existence of the β phase is widened to the low Al side, so that the cold workability is remarkably enhanced, and the production becomes easy. If the amount of the Mn element is less than 5% by weight, satisfactory workability cannot be obtained, and a β single phase region cannot be formed. If the addition amount of the Mn element exceeds 20% by weight, superelasticity cannot be obtained, which is not preferable. The preferred Mn content is 8 to 12% by weight.

The Cu-based alloy having the above composition is excellent in hot workability and cold workability, and can be worked at a cold working rate of 20% to 90% or more. It can be easily formed.

In addition to the above components, the copper-based alloy of the present invention further comprises Ni, Co, Fe, Ti, V, Cr, Si, Nb,
One, two or more selected from the group consisting of Mo, W, Sn, Ag, Mg, P, Zr, Zn, B and misch metal can be contained. The total content of these elements is preferably 0.001 to 10% by weight, particularly
0.001 to 2% by weight is preferred. These elements exert an effect of increasing the strength of the copper-based alloy by refining the crystal grains while maintaining the cold workability. However, when the content of these elements exceeds 10% by weight, the martensitic transformation temperature is lowered, and the β single phase structure becomes unstable.

Ni, Co, Fe, Sn and Ag are effective elements for strengthening the base structure. The preferred contents of Ni, Fe and Ag are each 0.001 to 3% by weight. Co also refines the crystal grains by forming CoAl, but excessively reduces the toughness. The preferred content of Co is 0.00
1 to 2% by weight. The preferred content of Sn is 0.001 to
1% by weight.

[0018] Ti combines with the inhibitory elements N and O to form oxynitride. In addition, a boron is formed by the complex addition with B, crystal grains are refined, and the shape recovery rate is improved. The preferred content of Ti is 0.001-2% by weight.

V, Nb, Mo, and Zr have the effect of increasing the hardness, improve the wear resistance, and since these elements hardly form a solid solution in the matrix, they precipitate as bcc crystals, and the crystal grains are fine. It is an element effective for chemical conversion. V, Nb,
The preferred contents of Mo and Zr are each 0.001 to 1% by weight.

Cr is an element effective for maintaining wear resistance and corrosion resistance. The preferred content of Cr is 0.001 to 2
% By weight.

Si has an effect of improving corrosion resistance.
The preferred content of Si is 0.001 to 2% by weight.

Since W hardly forms a solid solution with the matrix, it has an effect of strengthening precipitation. The preferred content of W is 0.001 to 1% by weight.

Mg removes the inhibitory elements N and O and fixes the inhibitory element S as a sulfide, which is effective in improving hot workability and toughness. And cause embrittlement. The preferred content of Mg is 0.001 to 0.5% by weight.

P is used as a deoxidizing agent and has an effect of improving toughness. The preferred content of P is 0.01-0.5% by weight.

Zn has the effect of lowering the shape memory processing temperature. The preferred content of Zn is 0.001 to 5% by weight.

B has the effect of refining the crystal structure. Particularly, a composite addition with Ti and Zr is preferable. The preferred content of B is from 0.01 to 0.5% by weight.

Misch metal has an effect of making crystal grains fine. The preferred content of misch metal is 0.001 ~
2% by weight.

(2) Production method of copper-based alloy (a) Molding of copper-based alloy A copper-based alloy having the above composition is melt-cast and processed into a desired size of a tube or wire by hot rolling, cold rolling, drawing or the like. Shape, ribbon shape, etc. The copper-based alloy having the composition of the present invention is rich in hot workability and cold workability, and has a cold workability of 20% to 90%.
Or a processing rate higher than that is possible, and it can be easily formed into a very fine wire or the like.

(B) Solution treatment Next, the solution is heated at a temperature of 500 ° C. or more, preferably 600 to 900 ° C. to transform the crystal structure into a β single phase. After the heat treatment, the mixture is rapidly cooled at a rate of 50 ° C./sec or more to freeze the β single phase state. The quenching is carried out by putting it in a coolant such as water or by forced air cooling. If the cooling rate is less than 50 ° C./sec, precipitation of the α phase occurs, so that the β single phase crystal structure cannot be maintained, and the functional gradient decreases. The preferred cooling rate is at least 200 ° C./sec.

(C) Aging treatment As described in Japanese Patent Application No. 10-181268, the copper-based alloy used in the present invention is a functionally graded material. By aging treatment,
The copper-based alloy has a high stiffness end and a low stiffness end, and the stiffness can be reduced continuously or stepwise from the high stiffness end to the low stiffness end.

The aging treatment of the low rigid end is performed at a temperature of less than 250 ° C., and the aging treatment of the high rigid end is performed at a temperature of 250 to 350 ° C. The intermediate portion located between the low-rigid end and the high-rigid end is aged with a temperature distribution (temperature gradient) that changes continuously or stepwise from the heating temperature of the low-rigid end to the heating temperature of the high-rigid end. Perform processing.

If the heating temperature of the low-rigidity end is too low, β
The phase is unstable and the martensitic transformation temperature may change if left at room temperature. Conversely, the heating temperature is 25
When the temperature is 0 ° C. or higher, precipitation of the α phase occurs, and the difference in the functional characteristics from the high-rigidity end portion is reduced. The heating temperature of the low rigidity end is preferably 100 to 200 ° C.

If the heating temperature of the high-rigidity end is lower than 250 ° C., the crystal structure of the high-rigidity end cannot be sufficiently transformed into two phases of α-phase and Heusler phase, and the functional characteristics of the low-rigidity end and the low-rigidity end will be poor. The difference becomes smaller. On the other hand, when the heating temperature exceeds 350 ° C., the structure becomes coarse, and the functional properties such as yield strength and hardness are reduced.
The heating temperature of the high-rigidity end is preferably 280 to 320 ° C.

The difference between the heating temperature of the low-rigidity end and the heating temperature of the high-rigidity end is preferably at least 50 ° C., particularly preferably at least 80 ° C. If the difference between the heating temperature of the low-rigidity end portion and the heating temperature of the high-rigidity end portion is less than 50 ° C., the difference in rigidity between the two portions becomes small.

The aging time varies depending on the composition of the copper-based alloy, but is preferably from 1 to 300 minutes, particularly preferably from 5 to 200 minutes. If the aging treatment time is less than 1 minute, the effect of aging cannot be obtained, and if the aging treatment time exceeds 300 minutes, the structure becomes coarse and the mechanical properties as a material become insufficient.

The tubular, linear, and ribbon-shaped copper-based alloys thus obtained are functionally graded alloys and have a substantially β single-phase crystal structure, as described in Japanese Patent Application No. 10-181268. A high-rigid end substantially comprising two phases of an α phase and a Heusler phase; and the low-rigid end located between the low-rigid end and the high-rigid end. To a high-rigidity end from a middle portion where the crystal structure changes continuously or stepwise.

In the present invention, "the crystal structure is substantially β
“Consists of a single phase” means that the crystal structure is not only the β phase, but also a small amount of α phase and Heusler phase, and a small amount of TiB, ZrB, b
This includes the case of having intermetallic compounds such as V, Mo, Nb, and W in the cc phase, and NiAl and CoAl. It is preferable that the total ratio of the α phase and the Heusler phase is 5% by volume or less. α
When the sum of the proportions of the phases and the Heusler phase exceeds 5% by volume,
This is not preferable because the superelasticity and shape recovery of the low-rigidity end portion are significantly reduced, and the slope of the functional characteristics is reduced.

On the other hand, “the crystal structure substantially consists of two phases of α phase and Heusler phase” means not only the case where the crystal structure consists of only α phase and Heusler phase but also a small amount of β phase and a small amount of Heusler phase. V, Mo, Nb of TiB, ZrB, bcc phase,
This also includes the case where W or an intermetallic compound such as NiAl or CoAl is contained. The proportion of the β phase is preferably 10% by volume or less.

The phrase “the crystal structure changes continuously or stepwise” means that the ratio of the β phase in the structure and α
Phase and the proportion occupied by the Heusler phase means a continuous or stepwise change. By the aging treatment, the α phase and the Heusler phase are gradually precipitated from the β phase, and the higher the temperature of the aging treatment and the longer the aging treatment time, the larger the ratio of the precipitated α phase and the Heusler phase. Whether the crystal structure changes continuously or stepwise is determined by the setting of the temperature distribution and the treatment time during the aging treatment. If the aging treatment is performed in a short time with a stepwise temperature distribution, the crystal structure changes stepwise.

The low-rigidity end portion composed of β single phase is disclosed in Japanese Patent Application Laid-Open No. 7-6247.
As described in No. 2, it has shape memory properties and superelasticity. On the other hand, the high-rigidity end is a hard material that is difficult to bend, and has completely different functional characteristics from the low-rigidity end.
In the portion between the low-rigidity end and the high-rigidity end, the functional characteristic of the low-rigidity end changes continuously or stepwise from the functional characteristic of the high-rigidity end.

Note that the length of the low-rigidity end, the length of the high-rigidity end, and the change pattern of the rigidity in the intermediate portion are as follows.
It can be set arbitrarily according to the distribution of the heating temperature during the aging treatment.

When the characteristics of the low-rigid end and the high-rigid end are compared, the hardness of the low-rigid end and the hardness of the high-rigid end differ depending on the alloy composition, but the hardness of the low-rigid end is less than 350 Hv. And the difference in hardness between the low rigid end and the high rigid end is 20 Hv or more. The low-rigid end portion is made of a superelastic material, and its yield stress (that is, 0.2% proof stress) differs depending on the alloy composition, but is less than 400 MPa. The difference in yield stress between the low rigid end and the high rigid end is 50 MPa or more. Further, the low rigidity end is a shape memory material, and the shape recovery rate is 80% or more. On the other hand, the shape recovery rate of the highly rigid end is less than 15%, and there is almost no shape memory characteristic. The difference between the shape recovery ratios of the low rigid end and the high rigid end is 70% or more.

[2] Catheter Having Tubular Copper-Based Alloy The first catheter of the present invention is at least partially composed of a tubular copper-based alloy. The proximal end of the catheter has moderate rigidity, and the distal end has lower rigidity than the proximal end. The bending elasticity of the tubular copper-based alloy decreases continuously or stepwise from the proximal end of the catheter toward the distal end, and at least the distal end has superelasticity. Hereinafter, the catheter of the present invention will be described with reference to specific examples, but the present invention is not limited thereto.

(1) First Embodiment FIG. 1 is a schematic view showing an embodiment of the catheter of the present invention (FIG. 2 is a sectional view taken along the line AA ′ of FIG. 1).

The main body of the catheter 1 is made of a copper-based alloy pipe 2. The bending elasticity of the pipe 2 is reduced continuously or stepwise from the base end to the distal end. The length of each region can be arbitrarily set as desired. The copper-based alloy pipe is manufactured by first producing a thick pipe by casting or the like and then gradually reducing the diameter by rolling or drawing.

For convenience, the pipe 2 is divided into a base end 2a and an intermediate part 2b.
In the description, the base end 2a is a high-rigidity region, and the distal end 2c is a low-rigidity, super-elastic region. The intermediate portion 2b is composed of the region 2a and the region 2c.
And has an intermediate rigidity. Within each region, the stiffness may be uniform or the stiffness may be reduced toward the tip.

The copper base alloy pipe having such a rigidity inclination is
Molded by hot working and / or cold working as described above,
It is manufactured by holding at a temperature of 500 ° C. or more, then quenching, and further aging. In the aging treatment, a different heating temperature is applied to each region. The aging temperature of the base end 2a is preferably 250 to 350C. The aging temperature of the tip 2c is preferably less than 250 ° C. The aging temperature of the intermediate portion 2b is the aging temperature between the base end 2a and the tip 2c. When it is desired to incline the rigidity in each area, the temperature distribution of the aging treatment in each area may be set so that the temperature gradually decreases toward the tip.

(2) Second Embodiment FIG. 3 is a schematic view showing another embodiment of the first catheter of the present invention (FIG. 4 is a sectional view taken along the line BB 'of FIG. 3, and FIG.
CC ′ cross-sectional view of FIG.

The main body of the catheter 11 is a copper-based alloy pipe 1
Consists of two. The bending elasticity of the pipe 12 is reduced continuously or stepwise from the proximal end to the distal end similarly to the first embodiment. The tip 12c is tapered so that the outer diameter decreases toward the tip.

The catheter 11 may be the same as the catheter 1 of the first embodiment, except that the tip 12c is tapered.

(3) Third Embodiment FIG. 6 is a schematic view showing another embodiment of the first catheter of the present invention. The catheter 21 is the catheter 1
1 is bent at an angle of 90 to 150 °. Thereby, it can be easily inserted into a meandering or branched blood vessel.

In order to form a bend at the tip, the formed pipe may be bent at a predetermined angle and then subjected to a solution treatment and an aging treatment.

(4) Surface Treatment of Catheter In the first catheter of the present invention, Au, Pt, Ti, Pd, and T are applied to at least the surface of the copper-based alloy pipe of the catheter.
It is preferable to coat iN by plating, vapor deposition, or the like. Further, it is preferable to coat at least a part of the catheter with a resin such as polyethylene, polyvinyl chloride, polyester, polypropylene, polyamide, polyurethane, polystyrene, fluororesin, silicone rubber, or an elastomer thereof, or a composite material. These coating materials preferably further contain a contrast agent such as barium sulfate. It is preferable to coat the surface of the catheter with a lubricating substance such as polyvinyl pyrrolidone, maleic anhydride ethyl ester, and methyl vinyl ether maleic anhydride copolymer. Further, it is preferable to coat the surface of the catheter with an antithrombotic material such as heparin or urokinase.

[3] Catheter Having Copper-Based Alloy Reinforcement FIG. 10 shows an embodiment of the second catheter of the present invention (FIG. 1).
1 is a sectional view taken along the line FF 'in FIG. Carousel 5
Has a flexible tube main body 51, a hub 52 provided at a base end of the tube main body 51, and a soft tip 53 attached to a distal end. The tube body 51 is reinforced with a linear or ribbon-shaped copper-based alloy reinforcing material.
Note that the shape of the reinforcing material is not limited to a linear shape or a ribbon shape.

In the example shown in FIG.
Is composed of an inner layer 54, a braid 55 made of a Cu—Al—Mn-based alloy in an intermediate portion, and an outer layer 56. In the example of FIG. 11, the braid 55 includes eight thin metal wires made of a copper-based alloy, but the number of thin metal wires made of a copper-based alloy may be one or more. Instead of a braid, a thin wire made of a copper-based alloy may be arranged in the longitudinal direction of the catheter. Further, a coil made of a copper-based alloy thin wire may be used.

The reinforcing material made of a copper-based alloy reduces the bending elasticity continuously or stepwise from the base end to the tip. The proximal end is a high rigidity region, and the distal end is a low rigidity, superelastic region. The intermediate portion has a rigidity intermediate between the base end portion and the distal end portion. In each region, the rigidity may be uniform or may be changed (decreased) continuously or stepwise in the direction of the distal end.

Such a reinforcing material made of a copper-based alloy having an inclined rigidity can be manufactured by applying different heating temperatures to the respective regions during the aging treatment. The aging temperature at the base end is preferably 250 to 350 ° C. Further, it is preferable that the aging temperature at the tip is less than 250 ° C. On the other hand, the aging treatment temperature in the intermediate portion is a temperature between the two. When it is desired to incline the rigidity in each area, the temperature distribution of the aging treatment in each area may be set so that the temperature gradually decreases toward the tip.

In order to manufacture a catheter containing a reinforcing material, a method of extruding the reinforcing material together with the plastic resin constituting the tube body 51, or covering the inner layer 54 with the reinforcing material, and immersing the inner layer 54 in a solution of the plastic resin, A method of curing the resin may be used, but is not particularly limited in the present invention. .

In the second catheter of the present invention, the surface of the catheter is preferably coated with a lubricating substance such as polyvinylpyrrolidone, maleic anhydride ethyl ester, methyl vinyl ether maleic anhydride copolymer and the like. Further, it is preferable to coat the surface of the catheter with an antithrombotic material such as heparin or urokinase.

[0060]

EXAMPLE 1 Figure 1 (Fig. 2 A-A 'sectional view of FIG. 1) were prepared catheter shown in. The catheter 1 is composed of a super-elastic Cu-Al-Mn alloy pipe 2 having an outer diameter of 1.5 mm and an inner diameter of 1.4 mm. The pipe 2 has a proximal end 2 a, an intermediate part 2 b, and a distal end 2.
c, the bending elasticity is reduced stepwise, and the tip 2c
Is gradually becoming more flexible towards the tip.

The pipe 2 was formed as follows. Dissolving a copper-based alloy having a composition of 7.5 wt% Al, 9.9 wt% Mn, 2.0 wt% Ni, and 80.6 wt% Cu,
Solidified at an average cooling rate of 140 ° C./min, 2 mm in diameter,
It was cold-rolled into a tube having a wall thickness of 0.1 mm.

Then, after a heat treatment at 900 ° C. for 10 minutes,
Quenched in ice water. After cutting this pipe 2 to a predetermined length, the three locations of the base end 2a, the intermediate part 2b, and the tip 2c are respectively subjected to the following temperature conditions 2a: 300 ° C., 2b: 250
° C, 2c: Aging treatment was performed for 15 minutes with a temperature gradient in which the temperature decreased from 200 ° C to 150 ° C.

Further, the outside of the pipe 2 was covered with a coating layer 3 (a polyamide elastomer containing 40% by weight of barium sulfate as a contrast agent). The tip 2c is provided with a soft tip 4 to prevent damage to the blood vessel when inserted into the blood vessel.
Was installed. A lubricating layer (not shown) containing polyvinylpyrrolidone as a main component was formed from the intermediate portion 2b to the distal end in order to increase lubricity at the time of insertion into a blood vessel.

The catheter of Example 1 had rigidity at the proximal end and sufficient flexibility at the distal end, and could be used safely.

As in the present embodiment, it is possible to improve the flexibility without having a tapered tip portion, and also has the advantage that a micro-catheter having a small diameter can secure a wide lumen. During clinical use,
The injection of the contrast agent can be performed easily and safely.

Example 2 FIG. 3 (FIG. 4 is a cross-sectional view taken along the line BB ′ of FIG. 3, and FIG.
C ′ sectional view) was manufactured. The catheter 11 is composed of a super-elastic Cu-Al-Mn-V alloy pipe 12 having an outer diameter of 1.5 mm and an inner diameter of 1.4 mm, and the pipe 12 is stepwise formed into a proximal end 12a, an intermediate portion 12b, and a distal end 12c. After the heat treatment for lowering the bending elasticity, the distal end portion 12c is tapered so that the outer diameter decreases toward the distal end.

The pipe 12 was formed as follows. An alloy composed of 7.5% by weight of Al, 9.9% by weight of Mn, 2.0% by weight of V, and 80.6% by weight of Cu is melted, solidified at an average cooling rate of 140 ° C./min, and has a diameter of 2 mm and a thickness of 2 mm. It was cold rolled into a 0.1 mm tube.

The obtained pipe was heat-treated at 900 ° C. for 10 minutes, quenched in ice water, cut to a predetermined length, and the base end 12a, the intermediate part 12b, and the front end 12c were respectively separated into three places. 12a: 300 ° C, 12b: 250 ° C, 1
2c: An aging treatment was performed at 150 ° C. for 15 minutes.

Further, the outside of the pipe 12 is covered with a coating layer 13.
(A polyamide elastomer containing 40% by weight of tungsten as a contrast agent). Also at the tip,
In order to prevent damage to the blood vessel when inserted into the blood vessel, a soft tip 14 was attached. As in the first embodiment, the intermediate portion 12b
A lubricating layer containing polyvinylpyrrolidone as a main component was provided from the to the tip to increase the lubricity at the time of insertion into a blood vessel. The catheter of Example 2 had a rigid proximal end and a flexible distal end, and could be used safely and satisfactorily.

The catheter 11 has a wide range of design flexibility by changing the physical properties from the proximal end 12a to the distal end 12c and by tapering the distal end of the pipe 12 to obtain a wide degree of freedom in designing the hand. The flexibility of the tip can be compatible.

Example 3 A catheter shown in FIG. 6 was manufactured. The configuration of the catheter 21 is the same as that of the catheter 11 of Example 2, except that the distal end portion 22 of the catheter 21 is provided with a bending of about 120 °. As a result, it was possible to easily insert the blood vessel into a meandering or branched blood vessel.

Embodiment 4 FIG. 7 (FIG. 8 is a sectional view taken along the line DD ′ of FIG. 7, and FIG.
A PTCA catheter provided with the balloon shown in FIG. The catheter 31 was made of a Cu-Al-Mn alloy pipe 32 having an outer diameter of 2 mm and a wall thickness of 0.1 mm, and the rigidity was changed from the base end 32a to the middle part 32b and the front end 32c. The tip 32c is tapered,
Flexibility is further improved.

The pipe 32 was formed as follows. The composition is Al 7.5% by weight, Mn 9.9% by weight, Ni 2.0
Wt% and an alloy consisting of 80.6 wt% of Cu were melted and solidified and cast at an average cooling rate of 140 ° C./min.
m and cold-rolled into a tube having a wall thickness of 0.1 mm.

The obtained pipe was heat-treated at 900 ° C. for 10 minutes, quenched in ice water, cut to a predetermined length, and the three positions of the base end 32a, the intermediate part 32b and the end 32c were respectively set. 32a: 300 ° C, 32b: 250 ° C, 3
2c: An aging treatment was performed at 150 ° C. for 15 minutes.

The pipe 32 is plated with Au, and is joined to the coating layer 33 (polyamide elastomer tube) so as to cover the tip 32c. The coating layer 33 is provided with a balloon expansion hole 36 for expanding the balloon 35 and a through-hole 37 extending from the middle of the catheter 31 to the distal end to pass a guide wire so as to connect to the pipe 32.

The catheter 31 has a Cu—Al—Mn alloy pipe 32 almost up to the balloon portion.
While having sufficient pushability, it was excellent in flexibility and kink resistance, and could be used safely.

Example 5 A catheter shown in FIG. 10 (FIG. 11 is a sectional view taken along line FF ′ of FIG. 10) was manufactured. The carousel 101 includes a flexible tube main body 111, a hub 112 provided at a proximal end of the tube main body 111, and a soft tip 113 attached to a distal end. The tube body 111 is shown in FIG.
As shown in FIG. 1, the internal layer 114 and the Cu-Al-
It is composed of a braid 115 made of a Mn-based alloy and an outer layer 116.

The braid 115 contains 7.5% by weight of Al and 9% of Mn.
Cu-A having a composition of 9% by weight and 72.6% by weight of Cu
It consists of eight thin metal wires of diameter 0.035 mm made of an l-Mn base alloy.

The thin metal wire was formed as follows. The composition is Al
An alloy consisting of 17.5% by weight, Mn 9.9% by weight, Ni 2.0% by weight and Cu 80.6% by weight was melted, and an average of 1
Solidified at a cooling rate of 40 ° C./min to a diameter of 0.035 mm
Was cold rolled. Thereafter, after a heat treatment at 900 ° C. for 10 minutes, it was quenched in ice water.

The thin wire obtained in this manner is knitted to form a braid, and nylon 12 constituting the tube body 111 is formed.
Then, the braid of the fine wire was embedded in the tube main body 111 by extrusion.

Example 6 A catheter shown in FIG. 12 (FIG. 13 is a sectional view taken along line GG ′ of FIG. 12) was manufactured. The catheter 102 includes a tube main body 121, a hub 122 provided at a proximal end, and a soft tip 123 attached to a distal end. As shown in FIG. 13, the tube main body 121 includes an inner layer 124, a braid 125 made of a Cu—Al—Mn alloy in an intermediate portion, and an outer layer 126.

The braid 125 is composed of 8.0% by weight of Al, Mn1
The diameter of a Cu-Al-Mn-V-based alloy having a composition of 0.2% by weight, V1% by weight, and Cu 80.8% by weight is 0.1 mm.
It consists of 32 thin metal wires of 02 mm. From the base end to the front end of the thin wire formed and quenched in the same manner as in Example 5, three portions of the base end portion a, the intermediate portion b, and the front end portion are respectively provided.
Aging treatment was performed for 15 minutes under the conditions of a: 300 ° C., b: 250 ° C., and c: 150 ° C., and the rigidity of the portions a, b, and c of the tube main body 121 shown in FIG. It was adjusted to become.

The braid thus obtained was extruded together with the polyurethane resin in the same manner as in Example 5 to be embedded in the tube main body 121.

Example 7 A catheter shown in FIG. 14 (FIG. 15 is a partially enlarged view of FIG. 14) was manufactured. The catheter 103 is a tube body 1
31; a hub 142 provided at the base end; and a soft tip 133 mounted at the tip. As shown in FIG. 15, the tube main body 131 includes an inner layer 134, a braid 135 made of a Cu—A1-Mn alloy in an intermediate portion, and an outer layer 1.
36.

The braid 135 is composed of 8.0% by weight of Al, Mn1
The thickness of a Cu-A1-Mn-V-based alloy having a composition of 0.2 wt%, V1 wt%, and Cu 80.8 wt% is 0.1 mm.
It consists of two 01 mm ribbon-shaped pieces that spirally intersect. After molding and quenching in the same manner as in Example 5, from the proximal end to the distal end, by aging treatment for 15 minutes under the temperature conditions shown in Table 1, d, d of the tube main body 131 shown in FIG.
Adjustments were made so that the rigidity of the portions e, f, and g was changed from high to low. The hardness of each region of the braid 125 was measured with a micro Vickers hardness tester and is shown in Table 1.

Table 1 Area Aging Temperature Hardness (unit: Hv) d 300 ° C. 380 e 250 ° C. 290 f 200 ° C. 260 g 150 ° C. 270

The braid was buried in the tube body 131 by extruding it with nylon 12 in the same manner as in Example 5.

The braiding of the metal wires and the ribbon-like pieces of the catheters 101, 102, and 103 described above has a constant pitch. However, in order to further increase the rigidity of the incline, the pitch is densely arranged at the base end side. It can be sparsely knitted on the part side.

Example 8 A catheter shown in FIG. 16 (FIG. 17 is a sectional view taken along the line HH ′ in FIG. 16) was manufactured. The catheter 104 includes a tube body 141, a hub 142 provided at a proximal end, and a soft tip 143 attached to a distal end. The tube body 141 includes an inner layer 144 as shown in FIG.
It is composed of four thin wires 145 made of a Cu-Al-Mn-V-based alloy in the middle part and an outer layer 146.

A thin wire 145 made of a Cu-A1-Mn-V alloy, which was molded and quenched in the same manner as in Example 5, has h, i, and j three positions from the base end, respectively, at h: 300 ° C. ,
By adding an aging treatment for 15 minutes at a temperature of i: 250 ° C. and j: 150 ° C., the rigidity was reduced stepwise from the base end to the front end. Further, a taper process was applied to the tip from the middle of the i part to obtain flexibility.

Example 9 A catheter shown in FIG. 18 (FIG. 19 is a sectional view taken along the line II ′ of FIG. 18) was manufactured. The catheter 109 includes a tube main body 151, a Y-shaped hub 152 provided at a proximal end, and a balloon 154 attached to a distal end. As shown in FIG. 18, the tube main body 151 has a balloon expansion hole 157 and a thin wire 155 made of a Cu-A1-Mn alloy.
And an outer layer 156.

The thin wire 155 made of a Cu—Al—Mn alloy formed and quenched in the same manner as in Example 5 has k, 1, and m three positions from the base end, respectively, at k: 300 ° C.
Aging treatment was performed for 15 minutes at a temperature condition of l: 250 ° C. and m: 150 ° C., and the rigidity was reduced stepwise from the base end to the front end. Furthermore, the tapered portion was processed from the middle of the m portion to the tip portion 24 to obtain flexibility.

[0093]

The catheter of the present invention uses a tubular or linear Cu-Al-Mn-based alloy having good workability and functional gradient characteristics, continuously or stepwise changes the rigidity of the catheter, and further has a taper. By combining with processing and resin coating, a catheter can be designed and manufactured from a wide degree of design freedom, and it is possible to achieve both oppressive performance, twisting rigidity and flexibility in opposing performance, and it is excellent in operability and safety Can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an embodiment of the catheter of the present invention.

FIG. 2 is a sectional view taken along line AA ′ of FIG. 1;

FIG. 3 is a schematic view showing another embodiment of the catheter of the present invention.

FIG. 4 is a sectional view taken along line BB ′ of FIG. 3;

FIG. 5 is a sectional view taken along the line CC ′ of FIG. 3;

FIG. 6 is a schematic view showing another embodiment of the catheter of the present invention.

FIG. 7 includes a balloon (PTC) according to the present invention.
A) Schematic showing one embodiment of a catheter.

FIG. 8 is a sectional view taken along the line DD ′ of FIG. 7;

FIG. 9 is a sectional view taken along line EE ′ of FIG. 7;

FIG. 10 is a schematic view showing an embodiment of the catheter of the present invention.

11 is a sectional view taken along the line FF 'of FIG.

FIG. 12 is a schematic view showing another embodiment of the catheter of the present invention.

13 is a sectional view taken along the line GG ′ of FIG.

FIG. 14 is a schematic view showing another embodiment of the catheter of the present invention.

FIG. 15 is a partially enlarged view of FIG. 14;

FIG. 16 is a schematic view showing another embodiment of the catheter of the present invention.

FIG. 17 is a sectional view taken along line HH ′ of FIG. 16;

FIG. 18 is a schematic view showing another embodiment of the catheter of the present invention.

FIG. 19 is a sectional view taken along the line II ′ of FIG. 18;

[Explanation of symbols]

 1, 11, 21, 31 ... first catheter 2, 12, 22, 32 ... pipe 2a, 12a, 32a ... base end 2b, 12b, 32b ... Intermediate portions 2c, 12c, 32c ... Tip portions 3, 13 ... Coating layers 4, 14 ... ... Soft tip 35, 154 ... Balloon 36 ... Balloon expansion hole 37 ... Through holes 101, 102, 103, 104, 105-.Second catheters 111, 121, 131, 141, 151 , 143 ... Soft tip 114,124,134,144 ... Inner layer 115,125,135 ... Braid 145,155 ...・ Fine line 116 , 126, 136, 146, 156 ・ ・ Outer layer

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Ryosuke Kainuma 172-15 F Term, Tekurata-sha, Natori-shi, Miyagi F-term (reference) 4C081 AC08 BB03 BB05 BB07 BB09 BC02 CA022 CA032 CA042 CA052 CA062 CA072 CA132 CA162 CA212 CA232 CA272 CB052 CD062 CD22 CF24 CG03 CG04 CG07 DA03 DA04 DC03 DC04 EA02 EA03 EA04 EA06 EA12

Claims (16)

[Claims] 1. A catheter comprising at least a portion made of a metal tubular body, wherein at least a tip portion of the metal tubular body has a Mn content of 5 to 20% by weight, an Al content of 3 to 10% by weight, and a balance of Cu and unavoidable impurities. A catheter characterized by being an alloy. 2. The catheter according to claim 1, wherein
The copper-based alloy further comprises Ni, Co, Fe, Ti, V, C
r, Si, Nb, Mo, Sn, Ag, W, Mg, P, Z
A catheter comprising one or more selected from the group consisting of r, Zn, B and misch metal in a total amount of 0.001 to 10% by weight. 3. The catheter according to claim 1, wherein the bending elasticity of the metal tubular body decreases continuously or stepwise in a direction from a proximal end to a distal end of the catheter. And catheter. 4. The catheter according to claim 3, wherein
The metal tubular body is formed by hot working and / or cold working, rapidly cooled after being maintained at a temperature of 500 ° C. or more, and further heated continuously in a direction from the proximal end to the distal end of the catheter. It is obtained by aging treatment with a gradually decreasing temperature distribution, and the maximum temperature of the temperature distribution is 250 to 350
The catheter, wherein the lowest temperature in the temperature distribution is less than 250 ° C. 5. The catheter according to claim 1, wherein an outer diameter of at least a part of the metal tubular body is continuous or stepwise in a direction from a proximal end to a distal end of the catheter. A catheter characterized in that it has been reduced to: 6. The catheter according to claim 1, wherein the metal tubular body is made of Au, Pt, Ti, P.
d. A catheter coated with one of TiN and / or a resin. 7. A catheter in which a metal reinforcing material is included in at least a part of a catheter tube, wherein the metal reinforcing material is composed of 5 to 20% by weight of Mn, 3 to 10% by weight of Al, the balance being Cu and unavoidable impurities. A catheter comprising a copper-based alloy. 8. The catheter according to claim 7, wherein
The copper-based alloy further comprises Ni, Co, Fe, Ti, V, C
r, Si, Nb, Mo, Sn, Ag, Mg, P, Zr,
1 selected from the group consisting of Zn, B and misch metal
A catheter containing at least 0.001 to 10% by weight of one or more species. 9. The catheter according to claim 7, wherein the metal reinforcing material has a bending elasticity that decreases continuously or stepwise in a direction from a proximal end to a distal end of the catheter. Characterized catheter. 10. The catheter according to any one of claims 7 to 9, wherein the metal reinforcing material is formed by hot working and / or cold working, rapidly cooled after being maintained at a temperature of 500 ° C. or more, Further, the catheter is obtained by aging with a temperature distribution in which the heating temperature is continuously or stepwise reduced in a direction from the proximal end to the distal end of the catheter, and the maximum temperature of the temperature distribution is 250 to 350 ° C. Minimum temperature of distribution is 2
A catheter having a temperature of less than 50 ° C. 11. The catheter according to claim 7, wherein the metal reinforcing member is a thin metal wire, and one or more metal reinforcing members are arranged in a longitudinal direction of the catheter. 12. The catheter according to claim 7, wherein the metal reinforcing member is a metal wire fabric. 13. The catheter according to claim 7, wherein the metal reinforcing member is a coil. 14. The catheter according to claim 1, further comprising at least one balloon. 15. The catheter according to claim 1, further comprising a coating layer having lubricity on the surface during wet sliding. 16. The catheter according to claim 1, having an antithrombotic coating on the surface.