JP2000000297A - Guide wire and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to constitute a guide wire with one piece of a metallic glass wire of a large diameter by forming the guide wire of the metallic glass wire which has a supercooled liquid region exhibiting a viscous fluid state between a molten state and a solid state and having the diameter of a specified value. SOLUTION: The guide wire comprises a wire body portion 1 which has relatively high rigidity and flexibility, buckling resistance, on the like, and has the diameter of 200 to 2000 μm, a fine front end portion 2 which is smaller in the diameter than the diameter of this portion, exhibits more suppleness for its low elasticity and simultaneously hardly gives rise to the breakage and fissure by bending fatigue and a tapered connecting portion 3 which ties the wire body portion 1 and the front end portion 2 and converges gradually toward the front end side. The entire part thereof comprises one piece of metallic glass. The kinds of the metallic glass to be used are multiple element alloys of an iron system, zirconium system, or the like, three or more multiple element alloys of a noble metal system, or the like. The metallic glass which has a glass transition temp. and has a converted vitrification temp. and supercooled liquid region in a prescribed range or above is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a guide wire for a catheter using a large-diameter metallic glass wire, and more particularly, to a method for connecting a catheter for treatment or examination to a predetermined position in a blood vessel or other organs. The present invention relates to a guidewire for safely and quickly inserting the guidewire.

[0002]

2. Description of the Related Art Amorphous alloys have high strength, high corrosion resistance,
Amorphous alloys have been applied in fields that make effective use of these various properties since they were found to have properties such as excellent soft magnetism and high magnetostriction. However, Fe, Cu, N
In order to produce a solid of an amorphous alloy such as an i-base from a liquid, a cooling rate of about 10 ⁵ K / sec or more is required.
Applied materials are limited to thin-walled / small articles. The maximum critical thickness is about 100 μm for a ribbon, the maximum critical diameter is about 150 μm for a thin wire, and about 50 μm for a powder.

[0003] The application field of amorphous alloys and the material shape are closely related, thin ribbons are mainly used in the field of magnetic materials, thin wires are used in the field of strength materials and magnetic materials, and powders are used in the field of electromagnetic materials. Has been used. In order to provide an amorphous wire for use as a guide wire for a catheter, a wire having a diameter of at least 200 μm is required from the viewpoint of rigidity and flexibility.

[0004] Thus, attempts to directly produce a metal wire having a round cross section directly from a melt have been actively conducted.
Many process technologies have been devised. When focusing on the production of amorphous alloy wires with long circular cross sections, the technologies that have succeeded in producing such wires are glass coating prevention (Taylor method), melt drawing, and spinning in rotating liquid. There are obtained wire diameters of 5 to 30 μm,
It is reported that the diameter is in the range of 20 to 150 μm and 70 to 150 μm. As a technique for producing an extremely thin amorphous wire or a non-equilibrium crystal wire, a melt drawing method and a spinning method in a rotating liquid are generally used. ing.

Japanese Patent Laid-Open No. 1-99571 discloses an example of a guide wire using an amorphous wire. It is practically impossible to construct a guidewire with a wire, and a plurality of wires must be used by twisting, and the wire diameter is 150 μm.
The development of the above thick wire rod has been strongly demanded. However, in the above-described spinning-in-rotating-liquid spinning method and the melt drawing method, a thick amorphous alloy wire has not been obtained until now due to the following two problems.

One is that these techniques have a diameter of 200 mm.
Above μm, irregularities on the surface of the wire become large, and a wire having a uniform diameter cannot be obtained. This is considered to be time consuming until solidification of the molten metal. The other one has a diameter of 20
If it is 0 μm or more, the cooling rate of the wire becomes lower than the critical cooling rate required for producing an amorphous alloy, and the wire becomes a crystalline phase and becomes extremely brittle. A third reason is that the “supercooled liquid state” of the metallic glass used in the present invention does not exist in the amorphous metal itself. The “supercooled liquid state” will be described in detail in the detailed description of the present invention.

The properties required for a catheter guide wire are as follows. If a guide wire for an angiographic catheter is described as a representative example, first,
Insert the guide wire into the blood vessel through the introduction needle installed on the skin, operate the hand operation part of the main body part that is out of the body, and bend the tip part according to the bend or branch of the blood vessel while bending it Let go and reach a predetermined position.

During this time, in order to overcome the insertion resistance generated between the inserted guide wire and the inner surface of the blood vessel, the insertion portion of the main body of the guide wire must have some rigidity and flexibility along the blood vessel, so that it is flexible. Must be provided. Moreover, it is necessary to bend gently along the bend of the blood vessel even in the main body (there is also a very small radius of curvature such as a radius of 5 mm in the vena cava), and it has not only the rigidity but also the flexibility. Must be. The distal end of the guide wire must be advanced without trauma to the inner wall of the blood vessel while searching for the bend or branch of the blood vessel that is meandering intricately, and especially at the operation of the extracorporeal operation part. It must bend or bend by the intended amount in the direction in which it is made, and the tip portion is required to be more flexible than rigidity.

In the case where the guide wire is a general metal such as a piano wire or a stainless steel wire, if a flexible distal end portion is bent in accordance with a complicated blood vessel, plastic deformation occurs when a certain amount of deformation is exceeded. Incorrect operation may cause irreversible buckling or torsional deformation, and in cases of severe loss of blood vessel running properties, continuation of the treatment may not be possible. Further, with these general metals, if the thickness is made to a certain extent, the flexibility is lost and the rigidity is enhanced, and there is a possibility that the blood vessel may be broken.

[0010] In addition, those using a twisted wire of an amorphous wire having a diameter of about 150 µm at the maximum are excellent in flexibility, but have poor rigidity even if coated with a resin, and as a result, are not practical for a guide wire. It was poor.

[0011]

The problem to be solved by the present invention is as follows.
An object of the present invention is to make it possible to form a guide wire with one large-diameter metal glass wire, instead of a conventional thin-wire amorphous wire twisted wire, or a general metal such as a stainless wire or a piano wire.

[0012]

A guide wire (A) according to claim 1 has a supercooled liquid region (S) exhibiting a viscous flow state between a molten state and a solid state, and has a diameter of Is 200
It is formed of a metallic glass wire (6) having a size of from μm to 2000 μm. "

According to this, since the metallic glass has the supercooled liquid region (S), the processing in this region (S) is very simple, similar to glasswork. Then, if the processed portion is cooled at a speed higher than the critical cooling rate, this portion also reversibly returns to the solid metallic glass, and exhibits the indispensable properties of the solid metallic glass, such as flexibility and rigidity, which are essential for the guide wire. In addition, the thickness is 200 μm to 2000 μm.
Since it is sufficiently thick as m, a single guide wire (A) can be formed.

The guide wire (A) of [Claim 2] is a more detailed version of the composition of Claim 1, and is referred to as "Xa-Yb-Mc".
(X is Zr, Ti, Hf, La, Mg, Al, Fe, C
o, at least one metal selected from Ni and rare earth metals, and Y is Al, Zn, Ga, Si, B, C, Zr, H
f, one or more metals selected from Ti, Mo, Ta, Nb and rare earth metals, where M is Fe, Co, Ni, Pd,
One or more metals selected from Ag, Cu and rare earth metals, a = 50-80, b = 0-20, c = 0-50)
And has a diameter of 200 μm to 200 μm.
It is formed of a metal glass wire (6) of 0 μm ”.

The guide wire (A) of claim 3 is different from that of claim 2 in that a metallic glass having a composition based on a noble metal is used, and "Op-Qr-St (O is Pd, Pt,
One or more metals selected from Au and Ag, and Q is F
e, one or more metals selected from Co, Ni, Cu, S is one or more metals selected from P, C, Si, p = 20-85, r = 0-80, t = 10-30)
And has a diameter of 200 μm to 200 μm.
It is formed of a metal glass wire (6) of 0 μm ”.

The guide wires (A) according to the first to third aspects are all constituted by a metallic glass wire (6), and differ only in composition. And in each case, X,
When one kind of Y, M, O, Q, S is selected, a, b,
When c, r, and t are not 0, the alloy is a ternary alloy, and b,
When either c or r or t is 0, the alloy is a binary alloy. When at least one of X, Y, M, O, Q, and S is two or more kinds and b, c, r, and t are not 0, it is composed of a quaternary alloy or more. Will be.
In each case, it is significantly different from the conventional amorphous metal wire, and is excellent in flexibility and also excellent in rigidity and buckling resistance, and has properties optimal for use as a guide wire. In particular, precious metal based guidewires (A)
It has excellent biocompatibility and acts softly on patients with allergic constitution, and has the feature that it does not cause allergy.

[Claim 4] relates to conditions that can be a material of the guide wire (A) according to the present invention, and is characterized in that "the material shows a glass transition temperature". Although the glass transition temperature is also called a glass transition temperature or a vitrification temperature, in this specification, the glass transition temperature is used unified.

[Claim 5] further clarifies conditions that can be used as a material of the guide wire (A) according to the present invention.
"When the material is heated and heated from the solid state, it has a supercooled liquid-like region (S) before crystallization from the solid state".

[Claim 6] further restricts the condition of Claim 5, and is characterized in that "the supercooled liquid region (S) has a width of not less than the crystallization temperature and not less than 20K". I do.

[Claim 7] relates to the specific shape of the guide wire (A), which is characterized in that at least a part of the distal end portion (2) is formed to have a smaller diameter than the main body portion (1). And By doing so, the thin tip portion (2) becomes extremely pliable and easily bends even when it comes into contact with the inner wall of the blood vessel when passing through the blood vessel, so that it is not damaged. The main body portion (1) exhibits sufficient rigidity and flexibility, buckling resistance and operability of the material itself, and exhibits excellent properties as the guide wire (A).
Note that the tip portion (2) formed to have a small diameter may be a part of the tip portion (2) or may be the whole.

[Claim 8] relates to the property to be provided as the guide wire (A), "at least a part of the tip portion (2) is formed so as to have a lower elastic modulus than the main body portion (1). The feature is. Here, as one method for achieving a low elastic modulus, at least a part of the tip portion (2) is made thinner as described above, or another method may be used. The part with low elastic modulus is the tip part (2)
It may be part of the whole or the whole.

[Claim 9] is another specific shape of the guide wire (A), which comprises "a main body portion (1) having a large diameter and a tip portion having a small diameter.
The cross section of the connecting portion (3) between the connecting portion (2) and the connecting portion (3) gradually becomes thinner toward the distal end side. " In this way, the rigidity of the connecting portion (3) gradually decreases continuously as it goes in the distal direction, and the operability of the flexible distal portion (1) and the followability when passing through the blood vessel are improved. .

[Claim 10] is still another specific shape of the guide wire (A), which is characterized in that "the entire distal end portion (2) is gradually tapered toward the distal end side". In this case, the tip (2) is tapered,
(2) The waist can be given even a little, and the operability when passing through the blood vessel is improved.

[Claim 11] relates to a method for manufacturing a guide wire (A) according to the present invention, wherein "a molten metal glass material (4) is formed into a metal glass wire (6), and the metal glass wire (6) is formed. During or after forming, the supercooled liquid-like portion (S) of the metallic glass wire (6) is given a tension to reduce its cross-sectional area, and the reduced cross-sectional portion becomes the tip portion (2). And

According to this, while the molten metallic glass material (4) is being formed into the metallic glass wire (6), the rotating roll (8)
When tension is applied to the supercooled liquid-like portion (S) which is still in a viscous flow state immediately after it comes out of the molding member as in (9), this portion is elongated, the cross-sectional area is reduced, and the portion becomes thin. It can be the tip (2). Alternatively, a part of the material already formed into the metallic glass wire (6) is heated to a temperature range in which the supercooled liquid state is maintained without crystallization, and the supercooled liquid state part is heated.
(S) may be tensioned to reduce its cross-sectional area, so that the cross-sectionally reduced portion is the tip portion (2). This makes it possible to easily form a small-diameter tip portion.

[0026]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described sequentially according to the illustrated embodiment. 1 and 2 are front views of a guide wire (A) according to the present invention, in which a part of a main body portion (1) is omitted. FIG. 1 has relatively high rigidity and flexibility, and also has buckling resistance and the like.
A main part (1) having a diameter of 200 to 2,000 μm, and a thin tip part which is thinner than the main part (1) and has a lower elasticity than the main part (1), thereby exhibiting more flexibility and at the same time hardly causing a fracture due to bending fatigue. (2), the main body portion (1) and the distal end portion (2) are connected to each other, and the tapered connecting portion (3) gradually narrows toward the distal end side.
The book is made of metallic glass. The tip (2a) may be straight, may be spherical as shown in (a), may be curled or J-shaped as shown in (b), or ( The entire tip (2) as in (c)
It may be tapered gradually toward a). Generally, J type is used.

FIG. 2 shows another example of the guide wire (A), which is composed of a core material (G) and a cover coil spring material (g) [(a) and (b)], and a cover coil spring. There is [(c) (d)] when the material (g) is provided with the resin coat (i). In this case, at least the core material (G) is formed of the large-diameter metallic glass wire of the present invention. Of course, the cover coil spring material (g) can also be formed of a thin metal glass wire. At this time, hemispherical heads (2a1) and (2b) are formed at both ends of the core material (G) to stop the cover coil spring material (g).

The distal end portion (2) of the guide wire (A) shown in FIG. 1 and the core material (G) shown in FIG. 2 are both straight sections having substantially the same cross section from the connecting portion (3) to the distal end (2a). Although the case where it is formed in a shape is mentioned, the taper may be such that the cross section decreases to the tip (2a).

Although there are various types of metallic glass used in the present invention, iron-based, zirconium-based, magnesium-based, aluminum-based, and titanium-based materials such as Mg-Ln- (Ni , Cu, Zn), Ln-Al-T
m, Zr-Al-Tm, Fe- (Al, Ga)-(P, B, C, Si), Pd-Cu-Ni-P,
Fe- (Zn, Hf, Nb) -B (Ln = rare earth metal, Tm = IV to VIII
Ternary alloys such as ternary alloys), or quaternary alloys or ternary alloys of ternary or higher, and ternary alloys of noble metal ternary or higher, all of which are glass transitions. Temperature, and the converted vitrification temperature (Tg /
Tm) is 0.55 to 0.7, and the supercooled liquid region (Tx
-Tg) (S) having a width of 20 ° C to 127 ° C or more is generally targeted.

Iron-based, zirconium-based, magnesium-based,
This is commonly used for aluminum and titanium ternary alloys.
In the formula, Xa-Yb-Mc (X is Zr, Ti,
Hf, La, Mg, Al, Fe, Co, Ni and rare earths
One or more metals selected from metals, Y is Al, Z
n, Ga, Si, B, C, Zr, Hf, Ti, Mo, T
a, one or more metals selected from Nb and rare earth metals
M is Fe, Co, Ni, Pd, Ag, Cu and rare earth
One or more metals selected from the class of metals, a = 50-8
0, b = 0-20, c = 0-50)
Metal glass, Zr₆₀Al_Fifteen
Ni_{twenty five}, Zr₆₅Al_7.5Ni_27.5, Zr₅₅Al_TenNi_FiveC
u₃₀, Zr₅₅Ti_FiveAl_TenNi_TenCu₂₀, Zr₅₅Al_Ten
Cu₃₀Ni _Five, Zr₅₅Ti_FiveAl_TenCu_TenNi₂₀, Zr₅₅
A_TenCu₂₈Ni_FiveNb_Two, Fe₇₃Al _FiveGa_TwoP_TenC₆B_Four,
Fe₅₈Co₇Ni₇Zr_TenB₁₈, Fe₅₈Co₇Ni₇Zr_Three
Mo₇B₁₈, Fe₅₈Co₇Ni₇Mo_TenB₁₈, Fe₇₂Al_Five
Ga_TwoP_TenC₆B_FourSi₁, Fe_{Five 6}Co₇Ni₇Zr_TwoNb₈B
₂₀, La₅₅Al_{twenty five}Ni₂₀, Mg₅₅Cu_{twenty five}Y_Ten, Mg₆₀N
i₂₀La₂₀and so on.

In the noble metal system, if this is described by a general formula, Op-Qr-St (O is one or more metals selected from Pd, Pt, Au, and Ag, and Q is Fe, Co, N
i is one or more metals selected from Cu, S is P,
One or more metals selected from C and Si, and p = 20 to
85, r = 0~80, a metallic glass wire having a composition represented by t = 10 to 30), by raising a specific example, Pd _{40
Ni 40 P 20, Pd 40 Cu} 30 Ni 10 P 20, Pd 74 Cu 8 S
i _18, and the like.

The reduced vitrification temperature used for the metallic glass to be used in the present invention is an absolute number defined by (Tg / Tm) and is used as a parameter of a required cooling rate. The supercooled liquid region (S) is represented by ΔTx in FIG. 7, is defined by ΔTx = Tx−Tg, and indicates a parameter of the degree of stability of the supercooled liquid. Tg
Is the supercooled liquid area when the solid metallic glass is heated.
(S), and Tx is the temperature at which crystallization starts.

FIG. 7 is a graph showing a phase change when the solid metallic glass is heated and heated. As the temperature is increased (solid metallic glass → supercooled liquid exhibiting a viscous flow state →
(Crystal ⇒ molten liquid metal). Conversely, when the molten liquid metal is cooled to form metallic glass, as long as a sufficient cooling rate is satisfied, (molten liquid metal → supercooled liquid exhibiting a viscous flow state → solid metallic glass) (Crystal).

On the other hand, in the conventional amorphous,
As shown in FIG. 8, when the temperature of the solid amorphous body is increased by heating, the temperature changes from solid amorphous to crystalline to molten liquid metal as the temperature rises. Conversely, when cooling the molten liquid metal into metallic glass, as long as a sufficient cooling rate is satisfied, it becomes (molten liquid metal → solid amorphous) and exhibits a viscous flow state as in the present invention. There is no region in the supercooled liquid state). In this respect, the physical properties of the metallic glass of the present invention and the amorphous glass are definitely different.

Next, an example of the metallic glass according to the present invention (Z
Physical properties of (n-Al-Cu-Ni quaternary alloy) will be introduced. Thickness of the metallic glass wire rod 200 to 2000, a tensile strength of 180 kgf / mm ^2, elongation 2.3%, Young's modulus 11,000kgf / mm ^2, the Vickers hardness 500DPN, density 6.73 g / cm ^{3. The} crystallization temperature is 530 ° C. and the specific resistance is 130 μΩcm.

Next, a method of manufacturing the guide wire (A) according to the present invention will be briefly described. The cooling block (10) has a pair of roll storage cavities (14)
Are formed, and disk-shaped rotating rolls (8) and (9) are rotatably housed. The rotating shaft (1) is attached to the rotating rolls (8) and (9).
2) are respectively inserted, are supported by bearings (15), and a pulley (16) is attached to a protrusion protruding from the cooling block (10), and is shown via a belt (17). Not connected to the drive unit.

A through hole (18) through which the metallic glass wire (6) passes is formed in the cooling block (10) in a portion below the opposed portion (23) of the rotating rolls (8) and (9). , Crucible (11) in the upper part
An insertion space (19) into which the nozzle (5) is inserted is formed. The cooling block (10) is divided from the center for processing and is fixed by bolts. In the present embodiment, the cooling block (10) is cooled (in the present embodiment, it is water-cooled, but other refrigerants can be used), so that the cooling path (20) is appropriately formed.

A concave groove (24) is formed on the outer periphery of each of the pair of rotating rolls (8) and (9). In the embodiment of the figure, since the cross-section is semicircular, the shape of the concave groove (24) portion joined at the opposing portions (23) of the rotating rolls (8) and (9) is circular, and the resulting metallic glass wire (6) A circular cross section can be obtained.

The material in the rotating rolls (8) and (9) is generally made of hardened or hard chrome plated tool steel in order to secure the strength. Copper is preferred. Rotating roll applied to the present invention
(8) (9) In the case of wire or rod, the diameter is 150 μm or more,
Although it can be applied up to a diameter of a thickness that can be made into a metallic glass, at present, it can be realized up to a diameter of about 5 mm due to the limitation from the metallic glass.

The diameter of the rotating rolls (8) and (9) used in the present invention is preferably as small as possible. The diameter is at most 100 mm. The distance (G) to the line (L) connecting (0 ′) is 40 mm. In the case of a diameter of 50 mm, the distance (G) is 20 mm, and in the case of a diameter of 10 mm,
Distance (G) is 4mm, << Diameter 10mm, Distance (G) 4mm >>
Is the preferred dimension in this embodiment.

The crucible (11) is a quartz tube having a thin nozzle (5) at the bottom, which can be raised and lowered. Crucible (11)
A high-frequency heating coil (21) is disposed around the periphery of the crucible (11) so as to heat the metallic glass having the composition described above. The inner diameter of the nozzle (5) is formed according to the thickness of the desired metal glass wire (6) (in other words, the width of the concave groove (24)), and is formed to about 150 μm to 5 mm. The appropriate thickness is used, but generally it is 1
mm is used. However, since the tip of the nozzle (5) is desired to be as close as possible to the groove (24), it is made thin and thin as long as it can withstand heat.

Immediately below the cooling block (10), a take-up drum (2
2) is arranged, and the drawn metallic glass wire (6)
Is to be wound up.

Thus, the crucible (11) held at the top
The metallic glass raw material having the above composition is inserted therein, and a high frequency heating coil (21) is applied to melt the metallic glass raw material by induction heating. (Of course, it may be melted by another method.) Then, the crucible (11) is lowered and the opposing portions (23) of the rotating rolls (8) and (9) are lowered.
The nozzle (5) is brought close to the vicinity, the crucible (11) is pressurized, and the molten metal glass (4) flows out toward the concave groove (24).

At this time, the temperature of the molten metal of the metallic glass at the outlet of the nozzle (5) is substantially equal to the melting temperature (Tm).
± 200 ° C ”. Usually, the melting temperature (Tm) or higher, but in the case of the present invention, the melting temperature (Tm) + about 30 ° C. may be sufficient because the distance (G) from the nozzle (5) is short. However, even if the melting temperature (Tm) or lower, the metallic glass used in the present invention is in a supercooled state, so that the outflow from the nozzle (5) is not impaired.

The metallic glass flowing out of the nozzle (5) becomes a viscous flow state or a liquid wire (6) and flows down while being cooled in the direction of the concave groove (24). The molten metal glass (4) flowing down contacts the rotating rolls (8) and (9) in a supercooled state (a syrup showing viscous flow) and rotates with as little external shock resistance or impact force as possible. Roll (8) (9) groove (2
It is formed into a rod or a line in 4).

The metallic glass wire (6) which exhibits viscous flow or liquid at the moment when it comes into contact with the rotating rolls (8) and (9) is quenched, passes through the crystallization region in a short time, and rotates.
After passing through (9), the area (S) <<
(23) is in the range of about 0.1 mm to 20 mm >>. In the range of the region (S), the viscosity is extremely high, and the region vitrifies and solidifies beyond the region (S). This is a characteristic point of the present invention.

Here, immediately before solidification into metallic glass in the region (S) without giving an impact, the metallic glass wire rod
When a tension is applied to (6), the portion expands and the cross section decreases. Therefore, this portion becomes the tip portion (2). After that, when the tension is gradually released, the cross section gradually becomes thicker and the taper
(3) is constituted. When the tension is completely released, the metallic glass wire (6) is drawn out with its original thickness, and this portion becomes the main body portion (1).

In this case, since the rotating rolls (8) and (9) are disposed in the cooling block (10), the rotating rolls (8) and (9)
Is transferred from the surface to the cooling block (10) side and is cooled from the surface. Also, rotating roll
(8) The contact between (9) and the cooling block (10) is made via a lubricant (25) such as carbon or boron nitride.

Next, a method of manufacturing the guide wire (18) from the metallic glass wire (6) will be described. The first method is to heat a part of the material already formed into the metallic glass wire (6) to a temperature range that does not crystallize and maintain a supercooled liquid state, and apply tension to the supercooled liquid part (S). The cross-sectional area is reduced, and the reduced cross-section is used as the tip (2).

Another method is to use a molten metallic glass material.
In the process of forming (4) into metallic glass wire (6), a rotating roll
(8) Immediately after exiting from a molded member as in (9)
The take-up drum (22) taking up (6) is separated from the cooling block (10) to apply tension to the supercooled liquid portion (S) which is still in a viscous flow state, and extends this portion (S). When this portion (S) is elongated, the cross-sectional area is reduced as described above and becomes thinner, and this portion can be used as the tip portion (2).

Since the properties of this metal are similar to those of glass, when a supercooled liquid portion (S) is given tension, it easily expands in a syrup state and is cooled at room temperature or at a cooling rate above the critical cooling rate at a refrigerant. It can be returned to solid metallic glass by cooling. (Example) As metallic glass, Zr ₆₀ Al ₁₀ Ni ₁₀ Cu
_{The 20} alloy was melted at 1300K, and a large-diameter metallic glass wire was formed using the wire-forming apparatus shown in FIG. Nozzle outlet temperature is 7
At 50K, the glass transition temperature (Tg) of the alloy was slightly higher than 651K. Since the distance (G) from the nozzle to the rotating roll (diameter = 10 mm) is very short at 4 mm, it is considered that there is almost no cooling of the molten metal during this period, and the rotating roll passing temperature is higher than the glass transition temperature (Tg) (750 K).
Slightly lower). Approximately 20m after rotating roll
After a distance of m, the glass transition temperature (Tg) became 651K, and the metal glass wire was obtained. Considering the temperature drop (37k = 750k-651k) after passing through the rotating roll and the distance (20 mm) required between them, the cooling rate during this period is estimated to be about 1000 k / sec. The cooling rate by the rotating roll is estimated to be 2.5 × 10 4 k / sec. The metal glass wire formed by this method is 0.5 mm, 1 m
At m and 5 mm, the tensile strength was 1600 megapascals, the elastic elongation was 1.9%, and the Vickers hardness was 510. Then, a part of the metallic glass wire is heated to 660K and returned to the supercooled liquid area, the heated part is stretched by applying tension, and then thinned, cooled, and cut into a required length to form a guide wire. .

[0052]

According to the present invention, since a large-diameter metallic glass wire is used for a guide wire, it cannot be obtained with a conventional thin-wire amorphous wire twisted wire or a general metal such as a stainless steel wire or a piano wire. It has become possible to impart flexibility, rigidity and flexibility to a guide wire. In addition, since this metallic glass has a special transient region of a supercooled liquid state, by heating a part of the metallic glass wire, the heated part is returned to a supercooled liquid state part exhibiting a viscous flow state. Alternatively, by applying tension to the supercooled liquid state part in the viscous flow state in the wire forming process, the part can be easily thinned or deformed,
There is the advantage that the formation of the guidewire is very simple. In addition, when a metallic glass having a composition based on a noble metal is used as a guide wire, it exhibits excellent characteristics of being less likely to cause a metal allergy in a patient even when inserted into a living body because of its excellent biocompatibility. .

[Brief description of the drawings]

FIG. 1 is a front view of a first embodiment of a guide wire according to the present invention.

FIG. 2 is a front view of a second embodiment of the guidewire according to the present invention.

FIG. 3 is a front sectional view schematically showing a metallic glass wire manufacturing apparatus according to the present invention.

FIG. 4 is a plan sectional view of FIG. 3;

FIG. 5 is an enlarged plan view of a rotating roll part of FIG. 4;

FIG. 6 is an enlarged cross-sectional view of a rotating roll part of FIG. 3;

FIG. 7 is a graph showing a phase change of the metallic glass used in the present invention when the temperature is raised.

FIG. 8 is a graph showing a phase change of a conventional metallic glass used in the present invention when the temperature is raised.

[Explanation of symbols]

 (1)… Main body part (2)… Tip part (3)… Connecting part (4)… Metal glass melt (5)… Nozzle (6)… Metal glass wire (7)… Nozzle outlet (8)… Rotating roll (9) Rotating roll (10) Cooling block (11) Crucible (12) Rotating shaft (13) Coolant circulation hole

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[Procedure amendment]

[Submission date] June 23, 1998 (1998.6.2)
3)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Brief description of drawings

[Correction method] Change

[Correction contents]

[Brief description of the drawings]

FIG. 1 is a front view of a first embodiment of a guide wire according to the present invention.

FIG. 2 is a front view of a second embodiment of the guidewire according to the present invention.

FIG. 3 is a front sectional view schematically showing a metallic glass wire manufacturing apparatus according to the present invention.

FIG. 4 is a plan sectional view of FIG. 3;

FIG. 5 is an enlarged plan view of a rotating roll part of FIG. 4;

FIG. 6 is an enlarged cross-sectional view of a rotating roll part of FIG. 3;

FIG. 7 is a graph showing a phase change of the metallic glass used in the present invention when the temperature is raised.

FIG. 8 is a graph showing a phase change at the time of temperature rise of an amorphous used in a conventional example .

[Description of Signs] (1) Body part (2) Tip part (3) Connecting part (4) Metal melt (5) Nozzle (6) Metal wire rod (7) Exit of nozzle ( 8) Rotating roll (9) Rotating roll (10) Cooling block (11) Crucible (12) Rotating shaft (13) Coolant circulation hole

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Zhang Tong 3-17-30, Kongozawa, Taihaku-ku, Sendai, Miyagi Prefecture (72) Inventor Noboru 1-2, Morishita Shimo-Aiko, Aoba-ku, Sendai, Miyagi Japan In-company (72) Inventor Shin Satoshi Wang 1-2 Morishita, Shimo-Aiko, Aoba-ku, Sendai-shi, Miyagi Japan Material Co., Ltd. (72) Inventor Yuji 1-2, Shimo-Aiko, Morishita, Aoba-ku, Aoba-ku, Sendai, Miyagi Japan Material Inside (72) Inventor Kazuya Sato 1-2 Morishita, Shimo-Aiko, Aoba-ku, Sendai, Miyagi Japan Inside (72) Inventor Takashi Kurosaka 1-2, Morishita, Shimo-Aiko, Aoba-ku, Sendai, Miyagi Japan Material Co., Ltd. F term (reference) 4C081 AC08 BA13 BB07 BB08 CG01 CG03 CG04 CG05 CG06 CG07 CG08 DA04 DB01 DC12 EA03 EA04

Claims (11)

[Claims] 1. A supercooled liquid region which exhibits a viscous flow state between a molten state and a solid state, and has a diameter of 200 μm.
A guide wire formed of a metallic glass wire having a size of about 2000 μm. 2. Xa-Yb-Mc (X is Zr, Ti, H
f, La, Mg, Al, Fe, Co, Ni and at least one metal selected from rare earth metals, and Y is Al, Zn,
Ga, Si, B, C, Zr, Hf, Ti, Mo, Ta,
At least one metal selected from Nb and rare earth metals,
M is one or more metals selected from Fe, Co, Ni, Pd, Ag, Cu and rare earth metals, and a = 50 to 80,
b = 0-20, c = 0-50)
A guide wire formed of a metallic glass wire having a diameter of 200 μm to 2000 μm. 3. Op-Qr-St (O is Pd, Pt, A
u, one or more metals selected from Ag, and Q is Fe,
One or more metals selected from Co, Ni, and Cu;
Is one or more metals selected from P, C and Si, and p =
20 to 85, r = 0 to 80, t = 10 to 30), and is formed of a metallic glass wire having a diameter of 200 µm to 2000 µm. 4. The guidewire according to claim 1, wherein the material has a glass transition temperature. 5. The guide wire according to claim 1, wherein when the material is heated from a solid state to a heated state, the guide wire has a supercooled liquid state region until the material is crystallized from the solid state. A guide wire. 6. The guidewire according to claim 5, wherein the supercooled liquid region has a width of not less than a crystallization temperature and not less than 20K. 7. The guidewire according to claim 1, wherein at least a part of the distal end portion is formed to have a smaller diameter than the main body portion. 8. The guidewire according to claim 1, wherein at least a part of the distal end portion is formed to have a lower elastic modulus than the main body portion. 9. The guide wire according to claim 1, wherein a cross section of a connecting portion between the large-diameter main body portion and the small-diameter distal end portion gradually becomes thinner toward the distal end side. Guidewire to feature. 10. The guidewire according to claim 1, wherein the entire distal end portion becomes gradually thinner toward the distal end side. 11. A molten metal glass is formed into a metallic glass wire, and during or after the forming of the metallic glass wire, tension is applied to a supercooled liquid portion of the metallic glass wire to reduce its cross-sectional area. A method for manufacturing a guidewire, characterized in that the reduced portion is a tip portion.