WO2002014577A1

WO2002014577A1 - Method for manufacturing cylindrical thin-wall metal member

Info

Publication number: WO2002014577A1
Application number: PCT/JP2001/005817
Authority: WO
Inventors: Shuichi Miyazaki; Takashi Kawabata; Kaneto Shiraki
Original assignee: Japan Lifeline Co., Ltd
Priority date: 2000-08-04
Filing date: 2001-07-04
Publication date: 2002-02-21

Abstract

A method for manufacturing a cylindrical thin-wall metal member, which comprises a step of depositing a metallic thin film (40) on at least the surface of the perimeter of a core material (100) by the vapor phase growth method such as spattering and a step of removing the core material (100) and thus leaving the metallic thin film (40).

Description

Leaking field

The present invention relates to a method of forming a cylindrical member which can be reduced in thickness to, for example, several tens of microns or less, and has no mechanical connection portion and excellent mechanical strength.

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Light

For example, for a device such as a catheter, a resin tube is used for

However, for medical use, a thinner tube is required. For this reason, there is a problem that the strength of the tube in the body fat direction is increased and the push-in characteristics (pushability) are deteriorated. Therefore, although the tube that constitutes the catheter is made of a gold tube, it is difficult for a normal gold tube to insert into a tortuous site such as a blood vessel because it lacks flexibility 1 mm. It is.

Therefore, it has been tested that a tube constituting a catheter or the like is made of a superelastic alloy such as a nickel-titanium alloy.

Conventionally, as a method of forming a tube of gold such as a nickel-titanium alloy, there has been proposed a method in which a gold sickle is bent into a tube shape, and the joint is seam-welded to increase the workability. However, on this trip, there is a limit to the thinness of the tube, and the strength of the seam weld becomes a problem, and the tube is vulnerable to bending.

In addition, it is known that the metal tubing can be removed by means such as push-out and pull-out. However, even with this method, there was a limit to the thinning of the tube, and there was a limit to its use. Disclosure of the invention

The present invention has been made in view of such difficulties. For example, a gold metal pipe that can be reduced in thickness to several tens of microns to 1¾K and has no seam welds and excellent mechanical strength. It is an object of the present invention to provide a Sit method capable of easily manufacturing a shaped member. In order to achieve the above object, the thin-walled cylindrical member according to the present invention comprises a step of depositing a gold Jffii film on at least the outer peripheral surface of the core material by a vapor phase growth method, Removing and leaving the lifted J 金 film.

Knitting metal thin film with pattern power [! After performing laser cutting (for example, laser cutting), the knitting core material may be removed. Alternatively, after forming a resist pattern of a predetermined pattern on at least the outer peripheral surface of the knitting core material, and excluding the resist film with the HJt constant pattern, at least on the outer peripheral surface of the knitting core material by the phase growth method. A gold film may be deposited, and then the core material and the resist film may be removed.

Furthermore, the male member of the thin-walled cylindrical member according to the present invention is:

A step of forming a resist film of a predetermined pattern on at least the outer peripheral surface of the core material; a step of removing the self-core material and leaving a resist film of an r! HH / f constant pattern;

and (ii) depositing a metal thin film corresponding to the predetermined pattern of the resist film on at least the peripheral surface of the resist film having the predetermined pattern by a vapor phase epitaxy method.

In these cases, a thin metal tubular member made of a patterned gold film can be obtained.

In the present invention, the shape of the tubular member is not particularly limited, and may be a cylindrical tube, a rectangular tube, a polygonal tube, a bottomed tube, or the like. These tubular members are: Turn-processed material may be used.

In the present invention, the solid phase growth method is preferably a sputtering method, and more preferably a magnetron sputtering method. By these methods, in particular, a thin metal tubular member having a memory characteristic or a characteristic characteristic such as nickel-titanium alloy can be easily manufactured.

In the present invention, it is preferable that the braided metal thin film has special memory or superelastic properties. The metal thin-walled cylindrical member made of a gold film having these characteristics can be easily inserted even into a bent part, and the force is low. Because of its excellent sashability, it can be particularly suitably used as an optional device.

In addition, nickel-titanium, iron-manganese-silicon, Examples thereof include a copper-aluminum-nickel system and an amorphous metal system. In the present invention, “Na” means that the range of recoverable bullets is large, for example, as large as 1% to 10%. It also includes the large elasticity of the fastener. In addition, Nana metal is

The elastic modulus in the region is extremely small compared to the elastic modulus of iron and stainless steel, and is excellent in flexibility. Simple translation of 酾

Hereinafter, the present invention will be described based on an embodiment shown in the drawings.

1A and 1B are schematic cross-sectional views showing a process of a thin-walled tube according to one embodiment of the present invention.

FIG. 2 is a schematic view of a sputtering apparatus used for manufacturing a thin-walled tube. FIG. 3 is a schematic cross-sectional view of a main part of a sputtering apparatus according to another example.

FIG. 4 is a schematic diagram of a sputtering apparatus according to still another example,

FIG. 5 is a schematic view of a stent obtained by the i method according to another embodiment of the present invention, FIG. 6 is a schematic view of a main part showing a joint between the first stent element and the second stent element shown in FIG. 5,

7A to 7D are schematic cross-sectional views of main parts showing a process for manufacturing the stent shown in FIG. 5, and FIGS. 8A and 8B are cross-sectional views of main parts showing a use state of the stent. The best bear for carrying out the invention As shown in Fig. 1 and Fig. 1, the following describes the case of manufacturing a metal-M thin-walled tube as a metal thin-walled tubular member in the braided state. .

First, as shown in FIG. 1A, a core material 100 is prepared. The core material 100 has an elongated 开 e in the ^ direction, may be hollow or solid, and its cross-sectional shape is not particularly limited, and may be a circle, an ellipse, a square, a polygon, or another shape. . In the embodiment, the core material 100 is constituted by a solid rod having a circular cross section.

The material of the core material 100 is not particularly limited as long as it is a material that can be obtained from the metal film 40. It is not limited to water-soluble materials, low-temperature materials, or decomposable materials, and Nobuha diameter materials.

Examples of the f-capacitive material include, but are not particularly limited to, for example, sezolellose derivatives such as carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, polymethacrylic acid, sodium polyethylene sulfonic acid, polyethylene oxide, and polyvinyl acetate. Is done.

The low-temperature decomposable material is not particularly limited. For example, polylactic acid, polycarbonate, starch / polyvinyl alcohol, poly-3-hydroxybutylate (polyester), polyglycol, etc. Examples thereof include acid and polyprolactone.

Further, the material of the cap diameter is not particularly limited, and examples thereof include resins such as polyethylene, polypropylene, and nylon, and PTFE coatings on copper surfaces.

The thickness and length of the core material 100 are determined according to the application of the tube to be obtained, etc., but in the present real fiber, the outer diameter of the core material 100 is 2mra ^ below.で> Good in diameter.

Next, in the male in the manner, a gold coating film 40 is formed on the outer peripheral surface of the core material 100. In the embodiment, the metal thin film 40 is formed on the outer peripheral surface of the core material 100 using the magnetron sputtering apparatus 70 shown in FIG.

The magnetron sputtering apparatus 70 shown in FIG. Inside the soul 72, there is a crane, and a setting table 76 on which a target 74 is set. Outside the vacuum body 72, magnetron magnets 78 and 80 for providing lines of magnetic force to the target 74 are arranged.

Also, above the target 74 inside the rectilinear chamber 72, the core material 100 is rotated by the rotation holding device 82 so that the core material 100 is rotatably arranged around its axis. One end of 00 is held. By performing the magnetron sputtering while rotating the core material 100 around the vehicle core by the rotation holding device 82, the gold β film 40 is formed on the evening peripheral surface of the core material 100. It is formed.

As the target 7 4, an alloy target may be used. A plurality of metal targets may be placed in a plurality of IKs. In the embodiment, a nickel-titanium alloy target or a combination of a nickel target and a titanium target is set on the mounting base 76.

The thickness of the gold film 40 formed on the outer peripheral surface of the core material 100 using the magnetron sputtering apparatus 70 shown in FIG. 2 is not particularly limited, but may be as thin as 5 m or less Tgffi. In the inflated state, the gold J¾ film 40 is formed of a nickel-titanium alloy.

Next, according to the method of the present embodiment, as shown in FIG. 1B, the core material 100 disposed inside the metal thin film 40 is removed. In the case where the core material 100 is formed as a rolled material, as shown in the figure, only the core material 100 is stretched in the axial direction and the evening is protected. Thus, the core material 100 is formed from the inside of the metal film 40. Further, when the core material 100 is formed as a water-soluble material, the core material 100 on which the metal thin film 40 is formed is immersed in water or the like. Is dissolved in water, leaving only the tubular metal thin film 40. Further, when the core material 100 is made of a biodegradable material, only the core material 100 may be replaced with nocteria, amylase or reno. —Only the tubular metal thin film 40 is left by performing biodegradation treatment using a secret such as zemo.

According to the method of thin-walled gold tubes related to the method, it is possible to manufacture thin-walled thin tubes of 1 oum r, and the tubes are seamless, have uniform physical characteristics, and have excellent mechanical strength. I have. In addition, according to the method of the 賴 M ^ state, a thin tube made of the metal thin film 40 having the property can be easily formed.

Such a thin tube can be easily inserted into a bent portion and has excellent pushability, so that it can be particularly suitably used, for example, as a device for a catheter tube or the like. The thin-walled tube can also be used for other purposes, such as a varicose vein TO needle, a shaft for a nosket force 1 / ^ forceps, a stent, a lacrimal tube, etc. .

金 of the thin-walled thigh tube according to the embodiment is ff according to the first embodiment. This is a modification of the il method of the Kinto thin-walled tube, and the spattering device used for the production male is configured as shown in FIG. 3. Will be explained.

As shown in FIG. 3, in the male according to the present embodiment, a pair of rotation-permissible sealing devices 84 are provided on the opposite side walls of the Mariyanagi room 72 of the sputtering device, Through 4, the core material 100 is held inside the process 72. As shown in FIG. 3, the core material 100 is rotatably held by a sealing device 84 inside the wing room 72, and is moved in the axial direction from right to left in the drawing. It's ok. The shearing device 84 is configured to be able to seal the inside of the polisher 72 irrespective of the rotational movement and the directional movement of the core material 100 around the axis.

The core material 100 is moved in the axial direction while rotating inside the bell 72, and the magnetron is the same as that of ^ of the former tern 1 real expansion. By performing the tooling, the gold coating film 40 shown in FIG. 1A can be formed on the outer peripheral surface of the core material 100 along the direction of the fat.

The other steps in the formal voice are the same as those in the ItflB ^ 1 embodiment, and the description thereof will be omitted.

^ The method for manufacturing a thin metal tube according to the embodiment is a modification of the let method for a thin metal tube according to the m1 embodiment, and the sputtering device "^" used for the manufacturing male has the configuration shown in the figure. Are similar to those of the first embodiment, and only different parts will be described.

As shown in FIG. 4, according to the Φ actual state, a supply roll 86 for the core material 100 and a take-up opening 88 are provided inside the true & l 2 of the sputtering apparatus. The rooster S is placed and the "^" of the core material 100 to be processed is positioned above the target 74 by the intermediate holding rolls 90 and 92. The supply roll 86 and the take-up opening 88 are Each of the core members 100 held by the rotating frame 94 and rotated in the opposite directions by the horse cheek motor 96 to be held between the intermediate holding rows 90 and 92, respectively. The core material 100 can be moved in the direction of the car irtf from the supply roll 86 to the take-up opening 88. It has become.

For this reason, the core material 100 held between 90 and 92 was subjected to magnetron sputtering in a fiber-like manner, and the outer periphery of the core material 100 shown in FIG. 40 will be overwhelmed.

The other steps in the method are the same as those in the m 1 embodiment, and the description thereof will be omitted.

In the case of the inflated state, a method of forming a medical stent using the method of the present invention will be described. Before describing the manufacturing male in detail, the configuration of the stent of the present embodiment will be described first.

As shown in FIG. 5, the stent 2 according to the present embodiment is a stent having a substantially cylindrical shape as a whole to be placed in a lumen of a living body, and has a first stent element 4 and a second stent element 6. The first stent element 4 is formed of a material that covers the circumference in the circumferential direction, has an expandable crown, and is hard to fluff after its outer diameter is expanded. The shape whose outer diameter can be expanded is not particularly limited. Specifically, the shape is a waveform shape, a valley shape, a sine's cosine curve shape, a zigzag shape, a zigzag shape, a zigzag shape, a sawtooth shape, and a pulse shape along the circumferential direction. , Or a combination thereof, or any other repetitive shape or design without a particular repeating pattern. Materials that are not easily crushed after expansion are not limited, but include metals such as stainless steel (for example, annealed suS316), gold, platinum, or alloys thereof. Is exemplified.

The second stent element 6 is a stent element for connecting the plurality of knitted 1 stent elements 4 arranged in the lean direction to the lean direction. It is made of elastic metal. Reactive metal has a large range of recoverable bounces, for example, 1% to 10% JiL.In the monomorphic region, it has the property that the force required for change is constant even if the strain increases. . Generally, a superelastic metal has an elastic modulus in the elastic region that is several times smaller than the elastic efficiencies of iron and stainless steel, and is excellent in flexibility. This second stent element 6 has the property of recovering to the original 开 e after stress ^ against bending deformation of 120 TOLh. preferable.

The width Wl and Z or thickness of the first stent element 4 is preferably 30 to 400 u ^, more preferably 50 to 100 Π1, and the tMW 2 and Z or thickness of the second stent element 6. Is preferably 20 to 10 and more preferably 30 to

60 m. The unit length L1 in the fat direction of the repeating unit constituting each first stent element 4 is not particularly limited, but is preferably 0.5 to 5 thighs, more preferably 0.8 to 2 thighs. The length L2 in the fat direction of the second stent element 6 is not particularly limited, but is preferably 0.5 to 5 thighs, and more preferably 1.5 to 3 thighs. It should be noted that the second stent element 6 is not necessarily a boat that is a spring parallel to the central axis of the stent, but may be a straight line, a curved line, or a combination thereof.

In the embodiment, the second stent elements 6 are arranged more sparsely in the circumferential direction than the first stent elements 4. For example, it is preferable to arrange 2 to 6 second stent elements 6 in the circumferential direction of the first stent element 4. Further, the second stent element 6 may connect the peaks of the repeating unit in the first stent element, may connect the valleys, or may connect the valleys and the valleys. You may connect them in the middle.

As shown in FIG. 6, a connecting portion of the first stent element 4 with the second stent element 6 is provided with a contact convex section 4 so that 6 a of the second stent element 6 is overlapped and connected. . This connection is performed by spattering based on a key manufacturing method.

The overall dimensions of the stent 2 are appropriately determined according to the purpose of use and the like, and are not particularly limited. For example, for use in coronary vein continuation, the outer diameter of the stent 2 when expanded is preferably 2 ~ 5 thighs, the direction length is 15 ~ 40 thighs. In addition, in the case of a stent for vascular graft, the length of the stent 2 when the stent 2 is expanded is preferably 3 to 10 females, and the axial length is 15 to 40 thighs. In addition, the length of the stent for vascularization is preferably 5 to 30 thighs in the evening when the stent 2 is expanded, and the length in the vehicle direction is 30 to 100 thighs.

The surfaces of the first stent element 4 and the second stent element constituting the stent 2 are covered with a plating film and / or a biocompatible coating film. This is to improve biocompatibility. Platinum or gold plating film is used for plating film. You can. Examples of the biocompatible coating film include, but are not particularly limited to, ordinary polymers used for (1) such as olefins such as polyethylene, nitrogen-containing polymers such as polyimide / polyamide, and siloxane polymers. Further, the coating film is not limited to a polymer, and may be carbonized or non-carbonized. It may be a coating film of a substance such as carbon such as ilolite carbon and diamond-like carbon. Further, the surface of the stent 2 may be made hydrophilic, or the surface of the stent 2 may be fixed with a biological component or a bacterium fj that prevents restenosis. The thickness of the film is not particularly limited, but the thickness of the plating film is, for example, 0.05 to 5 m, and the thigh of the biocompatible coating film is about 0.1 to 10 m, preferably, 0.5 to 5πι.

Next, a method for a swelling stent will be described.

First, as shown in FIG. 7A, a core material 100 is prepared. The material of the core material 100 is the same as that of the core material 1 oo of the liria i real style. Next, on the outer peripheral surface of the core material loo, a stainless steel first gold film 140 (for example, having a thickness of 50 to 400 m), which is a raw material of the first stent element, is knitted. It is formed by the same magnetron sputtering method as the new method.

Next, as shown in FIG. 7B, a first resist film 150 made of a photosensitive resin is applied to the outer peripheral surface of the first metal thin film, and the first resist film 150 is exposed. 5, and processed into a pattern corresponding to 1 stent element 4, and thereafter, the first gold film 140 was etched in accordance with the pattern of the first resist film 150, and the first Obtain the pattern of 1 stent element 4.

Next, after the first resist film 150 is removed, as shown in FIG. 7C, a second resist film 160 made of a photosensitive resin is exposed, and the second resist film 160 is exposed. Then, a pattern of the opening corresponding to the pattern of the second stent element 6 shown in FIG. 5 is formed on the second resist film 160. After that, magnetron sputtering is performed on the core material 100 on which the first stent element 4 and the second resist film 160 having a predetermined pattern are formed in the same manner as in the above-mentioned iff mode. As a result, a pattern corresponding to the opening of the second resist film 160, for example, 3C! A second metal film made of nickel-titanium (100% / m 1) is used. This second gold J¾ film is Stent element 6.

Thereafter, as shown in FIG. 7D, the second resist film 160 is removed in accordance with a standard method, and the core material 100 is stripped of stainless steel having the pattern shown in FIG. The result 2 is obtained.

Next, a usage example of the stent related to the lateral expansion will be described.

As shown in FIG. 8A, the stent 2 is first mounted on the outer periphery of the balloon portion 10 of the balloon catheter 12 in a contracted state in the vertical direction. It is inserted into a body cavity such as a blood vessel 20. After that, the stent, together with the balloon portion 10 of the norm catheter 12, pierces the inside of the blood vessel 20, which is bent 90 degrees with a liLB, and finally the stenosis portion 22 of the blood vessel 20. To reach. In the stent 2 according to the inflated state, the second stent element 6 mainly bends easily in accordance with the bending 开 of the blood vessel 20 and is positioned at the target stenosis part 22, and then the second stent element 6 returns to its original position. Restore shape. Accordingly, the flexibility of the stent 2 and the customization of the insertion are improved.c ₎ Thereafter, as shown in FIG. I do. Thereafter, only the balloon catheter 12 is withdrawn from the blood vessel 20 and only the expanded stent 2 is placed inside the expanded stenosis 22 to prevent stenosis. In the present embodiment, the first stent element 4 of the stent 2 is a portion that suppresses the force of the stenotic portion of the expanded 5Sf barley to return to its original state, and is made of a material that is not easily obtained. In addition, restenosis can be effectively prevented.

* According to the stent 2 according to the F state, the second stent element 6 easily bends in accordance with the bent shape of the body cavity when the stent 2 is inserted into the body cavity, and is located at the target stenosis. After that, the original likelihood is recovered. Therefore, the flexibility of the stent 2 to follow the bending and the introduction efficiency are improved. Also, the first stent element 4 in the stent 2 is a portion for suppressing the force of the stenotic portion of the enlarged 5 lf to return to its original state, and is made of a material which is not easily purified. Can be prevented by force.

According to the method according to the embodiment, it is possible to extremely easily select a stent having such characteristics.

Other shaping education Note that the present invention is not limited to the above-described embodiment, and can be variously modified within the scope of the present invention.

For example, in the first embodiment of the present invention, the climbing characteristic of nickel-titanium alloy is ^) a thin metal tube made of gold coating film 40 is fiber-woven, but according to the structure of the present invention, The memory characteristics can be made in the same manner for thin metal tubes made of gold film.

Further, according to the method of the present invention, it is possible to manufacture not only a tube but also a thin-walled bottomed cylindrical member such as an object having a bottom at one end. Further, in the present invention, the vapor phase growth method is not limited to magnetron sputtering, and ordinary sputtering, vapor deposition, and the like can be used. However, magnetron hattering is particularly effective for forming a thin cylindrical member made of a superelastic alloy such as a nickel titanium alloy.

As described above, according to the present invention, it is possible to easily produce a gold tubular member that can be reduced in thickness to, for example, several tens of microns or less, and has no seam welds and excellent mechanical strength. Can be manufactured.

Claims

The scope of the claims

1. depositing a metal thin film on at least the outer peripheral surface of the core material by vapor phase epitaxy;

tiff Manufacturing of thin-walled cylindrical members with a process of removing their own core material and leaving their own JKI film

2. Ri self-metal thin film. 2. The method of claim 1, wherein the core material is removed after the turning process.

3. After forming a resist pattern of a predetermined pattern on at least the peripheral surface of the fi-core material, at least the outer peripheral surface of the core material excluding the resist film of the predetermined pattern is coated with gold by a lightning phase growth method. 2. The thin-walled cylindrical member according to claim 1, wherein the core material and the resist film are deposited on the substrate.

4. a step of forming a resist film having a predetermined pattern at least around the core material,

Removing the knitting core material and leaving a resist film with a fiem constant pattern; and forming a metal thin film corresponding to the predetermined pattern of the resist film on at least the circumferential surface of the resist film with the predetermined pattern by vapor phase growth. Depositing;

At¾¾ of thin β-walled cylindrical member with

5. The method according to any one of claims 1 to 4, wherein the core material is at least one of the following materials: a tolerable material, a low-temperature orchid, a raw material, and a raw material. Nisshinno Gold is a method of certifying thin cylindrical members.

6. The method for producing a thin metal tubular member according to any one of claims 1 to 5, wherein the self vapor deposition method is a sputtering method.

7. The method according to claim 1, wherein the Ml self-metal thin film has a rippling property or a squeezing property.