JP2012066008A - Multiple structure balloon and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a noncompliant multiple structure balloon stably high in bursting pressure and excelling in affected part passing property, and a method for manufacturing the same.SOLUTION: The multiple structure balloon 10 includes a first balloon 14 with the outer surface formed of a polymeric material, and a second balloon 12 with the inner surface formed of a polymeric material and with the first balloon telescopically inserted therein. The multiple structure balloon 10 has a bonded part at which the outer surface of the first balloon 14 and the inner surface of the second balloon 12 are bonded at least in part. The bonded part is constituted of an interpenetrating network structure formed by mutual entanglement of molecules of the polymeric material composing the outer surface of the first balloon 14 and molecules of the polymeric material composing the inner surface of the second balloon 12.

Description

  The present invention relates to a multi-structure balloon and a method for manufacturing the same.

  Balloon catheters are used to dilate a stenosis or occlusion site in a vessel and improve blood flow when stenosis or occlusion occurs in a vessel such as a blood vessel. The balloon applied to the balloon catheter is expandable and treats the lesion site by expanding at the target location.

  For example, a balloon catheter is desired to be able to be easily inserted without damaging even a narrow stenosis, an eccentric stenosis, or a meandering stenosis, and the profile diameter should be as small as possible. There must be. On the other hand, even when applied to a calcified lesion that has become extremely hard, the balloon is required to have a high pressure strength in order to exert a sufficient expansion force without rupturing the balloon. Moreover, it is preferable to have a so-called non-compliant property that the balloon diameter hardly increases even when a high pressure is applied.

  In general, if the balloon is thickened, the pressure resistance increases, but the profile diameter increases, so there is a trade-off relationship that the affected area permeability decreases, and the affected area permeability and pressure resistance are harmonized. Attempts have been made to achieve a high balance.

  In general, to achieve high breaking strength with a thin film, it is effective to increase the molecular orientation of the polymer constituting the film. In the case of a balloon, as one means for increasing the molecular orientation, a method of increasing the expansion ratio when the balloon is blow-molded from a tubular parison can be considered. When molding a balloon of a certain size, the expansion ratio of the membrane can be increased and the molecular orientation can be improved by molding from a thin tubular parison rather than blow molding from a thick tubular parison. However, of course, by forming from a thin tubular parison, the film thickness of the balloon becomes thin, and the absolute strength as a balloon may be reduced.

  Here, if another balloon can be nested inside a thin balloon formed from a thin tubular parison, the necessary thickness can be ensured while maintaining the molecular orientation of the film. That is, the method of forming a multi-structure balloon from a plurality of tubular parisons is more effective than blow molding a balloon from a tubular parison formed by coextrusion molding as a technique for improving the molecular orientation of the balloon and increasing the pressure resistance. Is.

  For example, by forming a multi-structure balloon from a plurality of tubular parisons, the molecular orientation and pressure resistance of the balloon are improved (see, for example, Patent Documents 1 to 3).

  In addition, by providing a lubrication layer between the balloons of the multi-structure balloon, there are some that uniformize the stress distribution applied to each balloon and prevent some balloons from bursting at an early stage (for example, see Patent Document 4). .)

JP-A-4-231070 Japanese National Patent Publication No. 9-508558 Special table 2001-511022 gazette Special table 2009-519770

  However, in the multi-structure balloons according to Patent Documents 1 to 3, some balloons (only the inner balloon or the outer balloon) are scratched against a hard object such as a stent or a calcified lesion, If it ruptures early due to a cause such as a defect, the diameter of the remaining non-ruptured balloon increases rapidly. This is because the pressure applied when bursting must be supported by the other non-bursting balloon. It is not preferable that the diameter rapidly increases when the balloon is expanded, because it may cause excessive expansion of the blood vessel and serious damage to the blood vessel.

  On the other hand, in the multi-structure balloon according to Patent Document 4, the profile diameter increases due to the presence of the lubricating layer, and there is a problem that the affected part passage property is lowered.

  The present invention has been made to solve the above-described problems associated with the prior art, and provides a non-compliant multi-structure balloon having a stable and high bursting pressure and good disease-passability and a method for producing the same. With the goal.

The uniform phase of the present invention for achieving the above object is as follows.
A first balloon whose outer surface is composed of a polymeric material;
A multi-structured balloon having an inner surface made of a polymeric material and the first balloon telescopically inserted into the second balloon,
An adhesion site where the outer surface of the first balloon and the inner surface of the second balloon are at least partially adhered to each other;
The adhesion site is formed by entangled with the polymer material molecules constituting the outer surface of the first balloon and the polymer material molecules constituting the inner surface of the second balloon. It is a multi-structure balloon characterized by comprising an interpenetrating network structure.

Another aspect of the present invention for achieving the above object is as follows:
A multi-structure balloon having a first balloon whose outer surface is made of a polymer material, and a second balloon whose inner surface is made of a polymer material and in which the first balloon is telescopically inserted. A method of manufacturing
The first balloon and the second balloon are formed from a first tubular parison whose outer surface is composed of a polymer material and a second tubular parison whose inner surface is composed of a polymer material, And an adhesion step of forming an adhesion site where the outer surface of the first balloon and the inner surface of the second balloon are bonded at least in part,
The adhesion site is formed by entangled with the polymer material molecules constituting the outer surface of the first balloon and the polymer material molecules constituting the inner surface of the second balloon. A multi-structure balloon manufacturing method comprising an interpenetrating network structure.

  According to the multi-structure balloon according to the multi-structure balloon according to the uniform phase of the present invention and the multi-structure balloon obtained by the manufacturing method according to another aspect of the present invention, the multi-structure balloon having the first balloon and the second balloon, Compared to the case where it is composed of a single balloon, it has a high pressure strength and exhibits a good non-compliant property. Since the first balloon and the second balloon have an adhesion site and only one of the balloons is prevented from bursting at an early stage, the burst pressure can be stably increased. The adhesion site is an interpenetrating network formed by entangled with the polymer material molecules constituting the outer surface of the first balloon and the polymer material molecules constituting the inner surface of the second balloon. It has a structure, and the first balloon and the second balloon are firmly bonded without the need to provide an intermediate layer such as an adhesive and do not easily peel off. And the increase in the profile diameter is suppressed, so that it is possible to secure good affected area passage. That is, it is possible to provide a non-compliant multi-structure balloon having a stable and high bursting pressure and a good affected area passage and a method for producing the same.

  In addition, since the polyamide resin spreads between molecular chains and increases molecular mobility due to the presence of the non-crystallizing agent, in the presence of the non-crystallizing agent, the outer surface of the first balloon and the inner surface of the second balloon , The polyamide resin molecules constituting the outer surface of the first balloon and the polyamide resin molecules constituting the inner surface of the second balloon are entangled with each other, thereby facilitating the interpenetrating network structure. It can be reliably formed. Therefore, it is preferable to apply a polyamide resin as a polymer material constituting the outer surface of the first balloon and the inner surface of the second balloon.

  It is preferable to apply a phenol compound as an amorphizing agent for the polyamide resin. Since the phenol compound acts only on the pole surface, it does not affect the pressure resistance of the multi-structure balloon. In addition, 1,3-dihydroxybenzene or t-butylhydroxyanisole is particularly preferable because it can cause the amorphousness of the polyamide resin to remarkably form an interpenetrating network structure easily and reliably.

  In addition, in the manufacturing method of a multi-structure balloon, it is not limited to the form which forms a 1st balloon and a 2nd balloon simultaneously, It is also possible to shape | mold a 1st balloon and a 2nd balloon separately. is there.

It is sectional drawing for demonstrating the multi-structure balloon which concerns on embodiment of this invention. It is the schematic for demonstrating the catheter to which the multi-structure balloon shown by FIG. 1 is applied. It is sectional drawing of the front-end | tip part of the catheter shown by FIG. It is the schematic for demonstrating the use of the catheter shown by FIG. It is a flowchart for demonstrating the adhesion process in the manufacturing method of the multi-structure balloon which concerns on embodiment of this invention. It is the schematic for demonstrating to the application | coating process and insertion process which are shown by FIG. It is sectional drawing for demonstrating the biaxial stretch blow molding process shown by FIG. It is the schematic for demonstrating the modification 1 which concerns on embodiment of this invention. It is the schematic for demonstrating the modification 2 which concerns on embodiment of this invention. 6 is a graph for explaining a pressure resistance test result of the multi-structure balloon according to Example 1; 6 is a graph for explaining the pressure resistance performance test result of the multi-structure balloon according to Example 2; 6 is a graph for explaining a pressure resistance test result of a multi-structure balloon according to Comparative Example 1. 6 is a graph for explaining a pressure resistance test result of a multi-structure balloon according to Comparative Example 2.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  FIG. 1 is a cross-sectional view for explaining a multi-structure balloon according to an embodiment of the present invention, FIG. 2 is a schematic view for explaining a catheter to which the multi-structure balloon shown in FIG. 1 is applied, and FIG. FIG. 4 is a cross-sectional view of the distal end portion of the catheter shown in FIG. 2, and FIG. 4 is a schematic view for explaining the use of the catheter shown in FIG.

  The multi-structure balloon 10 according to the embodiment of the present invention is applied to, for example, the catheter 100 shown in FIG. The catheter 100 includes a distal end portion 120 on which the multi-structure balloon 10 is disposed on the outer periphery, a hub 140 located at the proximal end, and a hollow shaft tube 160 that connects the distal end portion 120 and the hub 140, It is used to improve the stenosis (or occlusion) 182 generated in the lumen 180 in the living body shown in FIG.

  The in-vivo lumen 180 is, for example, the coronary artery of the heart, and the stenosis 182 is treated by dilating the multi-structure balloon 10. The catheter 100 is not limited to a form applied to a stenosis portion generated in the coronary artery of the heart, but can be applied to a stenosis portion generated in other blood vessels, bile ducts, trachea, esophagus, urethra, and the like.

  A stent may be disposed on the outer periphery of the multi-structure balloon 10 as necessary. The stent is a medical device that holds the lumen 180 by being placed in close contact with the inner surface of the narrowed portion 182 and is configured to be expandable. The multi-structure balloon 10 is expandable, and a stent disposed on the outer periphery thereof can be expanded and placed.

  The stent is made of a biocompatible material, for example, nickel-titanium alloy, cobalt-chromium alloy, stainless steel, iron, titanium, aluminum, tin, zinc-tungsten alloy.

  The hub 140 has an injection port 142 as shown in FIG. The injection port 142 is used, for example, for introducing and discharging a pressurized fluid (for example, a liquid such as a physiological saline or an angiographic contrast agent) for expanding the multi-structure balloon 10. The constituent material of the hub 140 is, for example, a thermoplastic resin such as polycarbonate, polyamide, polysulfone, polyarylate, or methacrylate-butylene-styrene copolymer.

  The shaft tube 160 is formed with a guide wire port 166 (see FIG. 2). As shown in FIG. 3, the shaft tube 160 has an inner tube 162 and an outer tube 164 into which the inner tube 162 is inserted. The guide wire port 166 is used for inserting the guide wire 150 and projecting from the distal end portion via the shaft tube 160. The inner tube 162 communicates with the guide wire port 166 and extends through the multi-structure balloon 10 to the tip. Accordingly, the guide wire 150 inserted into the guide wire port 166 can protrude from the distal end of the catheter 100, and the inside of the inner tube 162 constitutes a lumen 161 for the guide wire.

  A coiled marker 170 is preferably attached to the inner tube 162. The marker 170 is made of a radiopaque material, and a clear contrast image can be obtained under fluoroscopy, so that the position of the distal end portion 120 of the catheter 100 can be easily confirmed. The radiopaque material is, for example, platinum, gold, tungsten, iridium, or an alloy thereof.

  The outer tube 164 is disposed outside the inner tube 162, and the lumen 163 formed by the space between the inner peripheral surface of the outer tube 164 and the outer peripheral surface of the inner tube 162 is connected to the injection port 142 of the hub 140. Communicate. The multi-structure balloon 10 is fixed in a liquid-tight manner on the outer periphery of the distal end portion of the outer tube 164, and the inside of the multi-structure balloon 10 communicates with the lumen 163. Accordingly, the pressurized fluid introduced from the injection port 142 passes through the lumen 163 and is introduced into the multi-structure balloon 10 so that the multi-structure balloon 10 can be expanded. A method for fixing the outer periphery of the distal end portion of the outer tube 164 and the multi-structure balloon 10 is not particularly limited, and for example, an adhesive or heat fusion can be applied.

  The constituent material of the outer tube 164 is preferably formed of a flexible material, such as polyethylene, polypropylene, polybutene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer, or these two. Polyolefins such as mixtures of at least species, soft polyvinyl chloride resins, polyamides, polyamide elastomers, polyesters, polyester elastomers, polyurethanes, thermoplastic resins such as polyurethane resins, silicone rubbers, latex rubbers.

  As the constituent material of the inner tube 162, the same material as the outer tube 164 or a metal material can be applied. The metal material is, for example, stainless steel, stainless stretchable alloy, or Ni—Ti alloy.

  The catheter shown in FIG. 2 is a so-called rapid exchange (RX) type balloon catheter, but the present invention can of course be applied to an over-the-wire (OTW) type balloon catheter.

  Next, the multi-structure balloon 10 will be described in detail.

  As shown in FIG. 1, the multi-structure balloon 10 includes a tubular large-diameter balloon 12 positioned on the outer side and a tubular small-diameter balloon 14 positioned on the inner side. It is composed of a double structure that is nested in the lumen. If necessary, the number of balloons inserted in a nested manner may be increased to have a triple structure or more.

  The large-diameter balloon 12 has an inner surface made of a polymer material, and the small-diameter balloon 14 has an outer surface made of a polymer material, and the outer surface of the small-diameter balloon 14 and the inside of the large-diameter balloon 12 It has an adhesion site where the surface adheres at least partially. The adhesion site is an interpenetrating network structure formed by entangled with the polymer material molecules constituting the outer surface of the small-diameter balloon 14 and the polymer material molecules constituting the inner surface of the large-diameter balloon 12. Consists of.

  Since the multi-structure balloon 10 includes the small-diameter balloon 14 and the large-diameter balloon 12, the multi-structure balloon 10 has a high pressure resistance and exhibits a good non-compliant property as compared with a case where the multi-structure balloon 10 is composed of a single balloon. The small-diameter balloon 14 and the large-diameter balloon 12 have an adhesion site, and one of the balloons is prevented from bursting early, so that the burst pressure can be stably increased. The adhesion site is an interpenetrating network structure formed by entangled with the polymer material molecules constituting the outer surface of the small-diameter balloon 14 and the polymer material molecules constituting the inner surface of the large-diameter balloon 12. Since the small-diameter balloon 14 and the large-diameter balloon 12 are firmly bonded without the need to provide an intermediate layer such as an adhesive and do not peel easily, the thickness is reduced (minimizing the wall thickness). It is possible to suppress the increase in the profile diameter, and thus it is possible to secure good diseased part passage.

  The polymer material constituting the outer surface of the small diameter balloon 14 and the inner surface of the large diameter balloon 12 is preferably a polyamide resin. The polyamide resin has high breaking strength, moderate flexibility, and the presence of the non-crystallizing agent expands the molecular chain and increases the molecular mobility. Therefore, the outer surface of the small-diameter balloon 14 in the presence of the non-crystallizing agent. And the inner surface of the large-diameter balloon 12 are brought into contact with each other so that the polyamide resin molecules constituting the outer surface of the small-diameter balloon 14 and the polyamide resin molecules constituting the inner surface of the large-diameter balloon 12 are mutually connected. This is because entanglement and mutual penetration network structure can be easily and reliably formed. In this case, an amorphizing agent is interposed in the interpenetrating network structure.

  The polyamide resin includes polyamide and polyamide elastomer. The polyamide that can be applied to the balloon material is not particularly limited as long as it is a polymer having an amide bond. For example, polytetramethylene adipamide (nylon 46), polycaprolactam (nylon 6), polyhexamethylene azide Homopolymers such as pamide (nylon 66), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecanolactam (nylon 11), polydodecanolactam (nylon 12) Caprolactam / lauryl lactam copolymer (nylon 6/12), caprolactam / aminoundecanoic acid copolymer (nylon 6/11), caprolactam / ω-aminononanoic acid copolymer (nylon 6/9), caprolactam / hexamethylene Diammonium azimuth Aromatic polyamides such as copolymers such as carbonate copolymers (nylon 6/66), copolymers of adipic acid and metaxylenediamine, or copolymers of hexamethylenediamine and m, p-phthalic acid Is mentioned.

  As the polyamide elastomer that can be applied to the balloon material, for example, a block in which nylon 6, nylon 66, nylon 11, nylon 12 or the like is a hard segment and polyalkylene glycol, polyether, aliphatic polyester, or the like is a soft segment. A copolymer is mentioned.

  Polyamide resins can be used alone or in admixture of two or more. The polyamide resin is not limited to a synthetic product, and a commercially available product can also be applied. For example, a commercially available product of polyamide is Grillamide L25 (manufactured by MSK Japan), and a commercially available product of polyamide elastomer is Grillflex ELG5660 (manufactured by MSK Japan).

  Since the outer surface of the large-diameter balloon 12 constitutes the outermost shell of the multi-structure balloon 10, it is preferable that the outer surface of the large-diameter balloon 12 is not easily damaged even when rubbed against a hard part such as a stent or a calcified lesion. Elastomers are preferred.

  The amorphizing agent that increases the molecular mobility by expanding the molecular chain of the polyamide resin is preferably a phenol compound. Polyamide resin is a crystalline polymer in which hydrogen bonds are formed between amide bonds of different polymer chains. However, it is partially amorphized by the action of a phenol compound and widens between the polymer chains. It becomes possible to contact each other with the polyamide resins that have spread between the polymer chains to form an interpenetrating network structure in which the respective polymer chains are intertwined in an indefinite shape. Since the phenol compound acts only on the extreme surface of the polyamide resin, it does not affect the pressure resistance of the multi-structure balloon 10.

  The phenol compound is not particularly limited as long as it causes the amorphousization of the polyamide resin. For example, 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol), 1,4-dihydroxybenzene ( Hydroquinone), 1,2,4-trihydroxybenzene, 1,6-dihydroxynaphthalene, 2,2′-biphenol, 4,4′-biphenol, t-butylhydroxyanisole. These may be used alone or in combination of two or more. In addition, 1,3-dihydroxybenzene or t-butylhydroxyanisole is particularly preferable because it causes the amorphousness of the polyamide resin to remarkably occur, so that an interpenetrating network structure can be easily and reliably formed.

  The balloon material is not limited to polyamide resin, and for example, polyvinyl chloride, polyolefin, polyamide, polyamide elastomer, polyimide, polyester, polyester elastomer, and polyurethane can be applied. It is also possible to improve the pressure strength by applying a composite material containing an inorganic compound such as carbon nanotube.

  Next, a method for manufacturing the multi-structure balloon 10 according to the embodiment of the present invention will be described.

  This manufacturing method generally includes a small-diameter balloon 14 and a large-diameter balloon 12 from a small-diameter tubular parison 24 whose outer surface is made of a polymer material and a large-diameter tubular parison 22 whose inner surface is made of a polymer material. And an adhesion step of forming an adhesion site where the outer surface of the small-diameter balloon 14 and the inner surface of the large-diameter balloon 12 are at least partially adhered to each other. The bonding site is an interpenetration formed by entangled with the polymer material molecules constituting the outer surface of the small-diameter balloon 14 and the polymer material molecules constituting the inner surface of the large-diameter balloon 12. It consists of a mesh structure.

  The small-diameter tubular parison 24 and the large-diameter tubular parison 22 are, for example, single-layer or multi-layer tubes formed by extrusion forming the small-diameter balloon 14 and the large-diameter balloon 12, respectively. The same as the balloon material. The small-diameter tubular parison 24 and the large-diameter tubular parison 22 are cut to a predetermined length suitable for a biaxial stretch blow molding process (biaxial stretch blow molding apparatus) described later.

  When a polyamide resin is applied as the parison material, in the bonding step, the bonding site is formed by bringing the outer surface of the small-diameter tubular parison 24 and the inner surface of the large-diameter tubular parison 22 into contact with each other through an amorphizing agent. In the interpenetrating network structure, an amorphizing agent is interposed. The amorphizing agent is preferably a phenol compound, particularly 1,3-dihydroxybenzene or t-butylhydroxyanisole.

  Next, the bonding process will be described in detail, taking as an example the case where a polyamide resin is used as the parison material and a phenol compound is applied as the amorphizing agent.

  FIG. 5 is a flowchart for explaining the bonding process in the method for manufacturing a multi-structure balloon according to the embodiment of the present invention, and FIG. 6 is a schematic diagram for explaining the application process and the insertion process shown in FIG. FIG. 7 is a cross-sectional view for explaining the biaxial stretch blow molding step shown in FIG.

  The bonding process includes an application process, an insertion process, and a biaxial stretch blow molding process.

  In the application step, a solution containing a phenol compound is applied to the outer surface of the small-diameter tubular parison 24 by, for example, a spray method (spray method). The solution containing the phenol compound may be applied to the inner surface of the large-diameter tubular parison 22, or may be applied to both the outer surface of the small-diameter tubular parison 24 and the inner surface of the large-diameter tubular parison 22. The application method is not limited to the spray method, and for example, a dipping method (dipping method), a printing method, and an impregnation sponge coating method can be applied. For example, the application to the inner surface of the large-diameter tubular parison 22 can be performed by suctioning a solution containing a phenolic compound with a negative pressure in the lumen of the large-diameter tubular parison 22.

  The solvent used in the solution containing the phenol compound is not particularly limited. For example, alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and t-butyl alcohol, N, N-dimethylformamide , N, N-dimethylacetamide, ethylene chloride, chloroform, acetone, tetrahydrofuran, dioxane, and these can be used alone or in combination of two or more. From the viewpoint of solubility, methanol and tetrahydrofuran are preferred.

  The concentration of the phenolic compound in the solution is not particularly limited as long as it does not affect the amorphousization, but is preferably 10 to 75% by weight, more preferably from the viewpoint of efficiently causing the amorphousization of the polyamide resin. Is 20 to 50% by weight.

  In the insertion step, the small-diameter tubular parison 24 is inserted into and closely adhered to the lumen of the large-diameter tubular parison 22 to form the double structure 20 (see FIG. 6). At this time, when the difference between the inner diameter of the large-diameter tubular parison 22 and the outer diameter of the small-diameter tubular parison 24 is small, the inner diameter is increased (expanded) by introducing gas into the lumen of the large-diameter tubular parison 22, The insertion can be facilitated by reducing (reducing) the outer diameter by extending the tubular parison 24 in the axial direction. When the difference between the inner diameter of the large-diameter tubular parison 22 and the outer diameter of the small-diameter tubular parison 24 is large, for example, by applying blow molding using a cylindrical mold, the inner surface of the large-diameter tubular parison and the small-diameter tubular It is possible to adhere to the outer surface of the parison.

  In the biaxial stretch blow molding process, for example, the double structure 20 is biaxially stretch blow molded using a pair of laminated molds 200 (see FIG. 7), so that the small diameter balloon 14 and the large diameter The balloon 12 is formed at the same time.

  More specifically, first, the double structure 20 is disposed inside the mold 200, both ends of the double structure 20 are closed, and heated to a temperature at which the polyamide resin (parison material) is plasticized. Then, by introducing the molding fluid into the double structure 20, the double structure 20 expands in the radial direction, and the cavity surface (inner wall) 202 of the mold 200 corresponding to the outer surface shape of the multi-structure balloon 10. Will be in close contact. The forming fluid is, for example, air or nitrogen.

  When the double structure 20 pressed against the cavity surface 202 is cooled (solidified) in a state in which it has the same outer surface shape as the outer surface shape of the multi-structure balloon 10 (see FIG. 7), the double structure 20 The forming fluid contained inside is discharged. And when the metal mold | die 200 is opened and a product is taken out, an unnecessary site | part will be cut suitably from the both ends, and it will become the multi-structure balloon 10. FIG.

  FIG. 8 is a schematic diagram for explaining the first modification according to the embodiment of the present invention.

  The large-diameter tubular parison 22 and the small-diameter tubular parison 24 are not limited to a form constituted by a single-layer tube. For example, the large-diameter tubular parison 22 can be a two-layer tube.

  The large-diameter tubular parison 22 composed of a two-layer tube can be formed by, for example, a coextrusion method. Moreover, since the material which comprises the inner layer 22B closely_contact | adhered with the outer surface of the small diameter tubular parison 24 and the material which comprises the outer layer 22A can be made different, the freedom degree of material selection improves.

  For example, since the outer layer 22A is the outermost surface of the double structure (three-layer structure) 30 that constitutes a double structure balloon, it can be easily rubbed against a hard object such as a stent or a calcified lesion. The material constituting the inner layer 22B is composed of a material that is not damaged (for example, polyamide elastomer), and is composed of a material having a relatively high strength (for example, polyamide), so that an appropriate balance between flexibility and strength is achieved. It is possible to take. Moreover, since the outer layer 22A does not adhere to the outer surface of the small-diameter tubular parison 24 (does not form an adhesion site), it is possible to apply a material unrelated to the amorphous effect. If necessary, the large-diameter tubular parison 22 can be composed of three or more layers of tubes, and the small-diameter tubular parison 24 can be composed of two or more layers of tubes.

  FIG. 9 is a flowchart for explaining the second modification according to the embodiment of the present invention.

  The small-diameter balloon 14 and the large-diameter balloon 12 are not limited to the form formed at the same time, and can be individually formed, for example. In this case, the bonding process includes, for example, a first molding process, an application process, an insertion process, and a second blow molding process.

  In the first molding step, the large-diameter tubular parison 22 is blow-molded, and the large-diameter balloon 12 is molded. In the application step, a solution containing a phenol compound is applied to the outer surface of the small-diameter tubular parison 24 by, for example, a spray method (spray method). In the insertion step, the small-diameter tubular parison 24 is inserted into the lumen of the large-diameter balloon 12.

  In the second blow molding process, the small diameter balloon 14 is formed by blow molding the small diameter tubular parison 24. At this time, the outer surface of the small-diameter tubular parison 24 and the inner surface of the large-diameter balloon 12 are brought into close contact with each other, whereby the large-diameter balloon 12 into which the small-diameter balloon 14 is inserted is formed.

  Next, the pressure resistance performance of the multi-structure balloon according to the embodiment of the present invention will be described.

  The balloon pressure resistance performance test was carried out by applying water pressure inside the multi-structure balloon and measuring the balloon diameter when a constant pressure was applied.

  The multi-structure balloon according to Example 1 was manufactured as follows.

  First, the large-diameter tubular parison was expanded by blow molding using a cylindrical mold. The large-diameter tubular parison is a two-layer tube having an inner layer made of nylon (grill amide L25) and an outer layer made of nylon elastomer (grill flex ELG5660), and the inner and outer diameters were 0.60 mm and 0.90 mm. . Moreover, the inner layer thickness and the outer layer thickness were 0.05 mm and 0.10 mm. The inner diameter and outer diameter of the large-diameter tubular parison after blow molding were 0.77 mm and 1.03 mm.

  And after apply | coating a tetrahydrofuran solution to the inner surface of a large diameter tubular parison, the small diameter tubular parison was inserted in the lumen | bore of a large diameter tubular parison, and the double structure was obtained. In the tetrahydrofuran solution, 25% by weight of 1,3-dihydroxybenzene (manufactured by Wako Pure Chemical Industries) was dissolved as an amorphizing agent. The small-diameter tubular parison was a single-layer tube made of nylon (Grillamide L25), and the inner and outer diameters were 0.45 mm and 0.65 mm.

  In order to bring the inner surface of the large-diameter tubular parison into close contact with the outer surface of the small-diameter tubular parison, the double structure was placed in a cylindrical mold and blow-molded. As a result, the inner and outer diameters of the double structure were 0.65 mm and 1.05 mm. And in order to shape | mold from a double structure to a multi-structure balloon, biaxial stretch blow molding (refer FIG. 7) was performed. The molded multi-structure balloon had an adhesion site, the outer diameter was 3.0 mm, and the film thickness (thickness) was 32 μm (average value of 20 samples).

  The multi-structure balloon according to Example 2 was manufactured as follows.

  First, the large-diameter tubular parison was expanded by blow molding using a cylindrical mold. The large-diameter tubular parison is a two-layer tube having an inner layer made of nylon (grill amide L25) and an outer layer made of nylon elastomer (grill flex ELG5660), and the inner and outer diameters were 0.43 mm and 0.87 mm. . The inner layer thickness and the outer layer thickness were 0.12 mm and 0.10 mm. The inner diameter and outer diameter of the large-diameter tubular parison after blow molding were 0.79 mm and 1.09 mm.

  And after apply | coating a methanol solution to the outer surface of a small diameter tubular parison, the small diameter tubular parison was inserted in the lumen | bore of a large diameter tubular parison, and the double structure was obtained. In the methanol solution, 50% by weight of t-butylhydroxyanisole (manufactured by Wako Pure Chemical Industries) was dissolved as an amorphizing agent. The small-diameter tubular parison was a single-layer tube made of nylon (Grillamide L25), and the inner and outer diameters were 0.49 mm and 0.73 mm.

  Next, biaxial stretch blow molding was applied to mold the double structure into a multi-structure balloon. The molded multi-structure balloon had an adhesion site, the outer diameter was 3.0 mm, and the film thickness (thickness) was 35 μm (average value of 20 samples).

  The multi-structure balloon according to Comparative Example 1 was manufactured as follows.

  First, a large-diameter tubular parison was placed in a cylindrical mold and expanded by blow molding. The large-diameter tubular parison is a two-layer tube having an inner layer made of nylon (grill amide L25) and an outer layer made of nylon elastomer (grill flex ELG5660), and the inner and outer diameters were 0.60 mm and 0.90 mm. . Moreover, the inner layer thickness and the outer layer thickness were 0.05 mm and 0.10 mm. The inner diameter and outer diameter of the large-diameter tubular parison after blow molding were 0.77 mm and 1.03 mm.

  Then, the small-diameter tubular parison was inserted into the lumen of the large-diameter tubular parison without applying an amorphizing agent to obtain a double structure. The small-diameter tubular parison was a single-layer tube made of nylon (Grillamide L25), and the inner and outer diameters were 0.45 mm and 0.65 mm. Next, biaxial stretch blow molding was performed in order to mold the double structure into a multi-structure balloon. The molded multi-structure balloon did not have an adhesion site, its outer diameter was 3.0 mm, and the film thickness (wall thickness) was 28 μm (average value of 20 samples).

  The balloon according to Comparative Example 2 was manufactured as follows.

  First, a single tubular parison having an inner layer made of nylon (grill amide L25) and an outer layer made of nylon elastomer (grill flex ELG5660) was formed by coextrusion. The inner and outer diameters were 0.49 mm and 1.10 mm, and the inner layer thickness and outer layer thickness were 0.28 mm and 0.03 mm.

  And in order to shape | mold the said single tubular parison into a balloon, biaxial stretch blow molding was performed. The outer diameter of the formed balloon was 3.0 mm, and the film thickness (wall thickness) was 35 μm (average value of 20 samples).

  10, FIG. 11, FIG. 12 and FIG. 13 are graphs for explaining the pressure resistance performance test results of the multi-structure balloons according to Example 1, Example 2, Comparative Example 1 and Comparative Example 2. The relationship with the balloon diameter is shown respectively.

  As shown in FIG. 10, the multi-structure balloon according to Example 1 has a burst pressure of 39 atm (average value of 20 samples), a high burst pressure, and a compliance characteristic of 0.007 mm / atm. (Average value of 20 samples), indicating a low value (good value), and a phenomenon of rapid increase in diameter during expansion was not detected.

  The multi-structure balloon according to Example 2 has the same performance as the multi-structure balloon according to Example 1, and as shown in FIG. 11, the burst pressure is 39 atm (average value of 20 samples), High burst pressure, compliance characteristic (average value of 20 samples) is 0.008 mm / atm, low value (good value), and sudden increase in diameter during expansion is detected There wasn't.

  On the other hand, the multi-structure balloon according to Comparative Example 1 shows a burst pressure of 39 atm (average value of 18 samples) and a high burst pressure in 18 samples out of 20 samples, and 0.009 mm / atm (average value of 18 samples). However, in two samples, the diameter rapidly increased during pressurization, and the phenomenon that the balloon burst early was observed. FIG. 12 shows the relationship between applied pressure and balloon diameter for one of the two samples whose diameters suddenly increased during pressurization (early ruptured). Note that the burst pressures of the two samples whose diameters increased rapidly during pressurization were 26 atm and 29 atm, respectively.

  Although the balloon according to Comparative Example 2 has a thickness equal to or greater than that of Example 1 and Example 2, the burst pressure is 37 atm (average value of 20 samples) as shown in FIG. The burst pressure is lower than that of Example 1, and the compliance characteristic is 0.016 mm / atm (average value of 20 samples). The expansion rate of the balloon diameter at the time of pressurization is larger than that of Example 1 and Example 2. . The balloon according to Comparative Example 2 did not detect a sudden increase in diameter during expansion.

  In addition, when the cross section of the balloon that was ruptured was observed, in the multi-structure balloon according to Comparative Example 1, there were many cases where a peeled portion was observed between the small-diameter balloon and the large-diameter balloon, and at first glance no peeling was observed. However, when touched, the contact surfaces of the two balloons were easily peeled off. On the other hand, in the multi-structure balloons according to Example 1 and Example 2, no peeling was observed between the small diameter balloon and the large diameter balloon, and they were firmly bonded.

  As described above, the multi-structure balloon obtained by the multi-structure balloon according to the present embodiment and the manufacturing method according to the present embodiment includes the small-diameter balloon and the large-diameter balloon, and thus is composed of a single balloon. Compared to the case, it has a high pressure strength and exhibits a good non-compliant property. Since the small-diameter balloon and the large-diameter balloon have an adhesion site and one of the balloons is prevented from bursting at an early stage, the burst pressure can be stably increased. The adhesion site consists of an interpenetrating network structure formed by entangled with the polymer material molecules constituting the outer surface of the small balloon and the polymer material molecules constituting the inner surface of the large balloon. Small diameter balloons and large diameter balloons are firmly bonded without the need for an intermediate layer such as an adhesive and do not easily peel off, making it possible to reduce the thickness (to minimize the wall thickness). By suppressing the increase in the profile diameter, it is possible to ensure good passability through the affected area. Therefore, the present embodiment can provide a non-compliant multi-structure balloon having a stable and high burst pressure and a good passage through the affected area, and a method for manufacturing the same.

  The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims.

10 multi-structure balloon,
12 Large diameter balloon,
14 Small diameter balloon,
20 double structure,
22 Large diameter tubular parison,
22A outer layer,
22B inner layer,
24 small diameter tubular parison,
30 double structure (three-layer structure),
100 catheters,
120 tip,
140 hub,
142 injection port,
150 guide wire,
160 shaft tube,
161 lumens,
162 inner pipe,
163 lumens,
164 outer tube,
166 guide wire port,
170 markers,
180 lumens,
182 Stenosis,
200 molds,
202 Cavity surface.

Claims (10)

A first balloon whose outer surface is composed of a polymeric material;
A multi-structured balloon having an inner surface made of a polymeric material and the first balloon telescopically inserted into the second balloon,
Having an adhesion site where the outer surface of the first balloon and the inner surface of the second balloon are bonded at least partially;
The adhesion site is formed by entangled with the polymer material molecules constituting the outer surface of the first balloon and the polymer material molecules constituting the inner surface of the second balloon. A multi-structure balloon characterized by comprising an interpenetrating network structure. The polymer material constituting the outer surface of the first balloon and the inner surface of the second balloon is a polyamide resin,
The adhesion site is such that the outer surface of the first balloon and the inner surface of the second balloon are brought into contact with each other via an amorphizing agent that widens the molecular chains of the polyamide resin to increase molecular mobility. Is formed by
The multi-structure balloon according to claim 1, wherein the decrystallization agent is interposed in the interpenetrating network structure. The multi-structure balloon according to claim 2, wherein the amorphizing agent is a phenol compound. The multi-structure balloon according to claim 3, wherein the phenol compound is 1,3-dihydroxybenzene or t-butylhydroxyanisole. A first balloon whose outer surface is composed of a polymeric material;
A method of manufacturing a multi-structure balloon having an inner surface made of a polymer material and the second balloon in which the first balloon is nested.
The first balloon and the second balloon are formed from a first tubular parison whose outer surface is composed of a polymer material and a second tubular parison whose inner surface is composed of a polymer material, And an adhesion step of forming an adhesion site where the outer surface of the first balloon and the inner surface of the second balloon are bonded at least in part,
The adhesion site is formed by entangled with the polymer material molecules constituting the outer surface of the first balloon and the polymer material molecules constituting the inner surface of the second balloon. A multi-structure balloon manufacturing method comprising an interpenetrating network structure. The polymer material constituting the outer surface of the first tubular parison and the inner surface of the second tubular parison is a polyamide resin,
In the adhering step, the adhering site is formed by connecting the outer surface of the first tubular parison and the second tubular parison through an amorphizing agent that widens the molecular chains of the polyamide resin and increases molecular mobility. Formed by contacting the inner surface,
The method for producing a multi-structure balloon according to claim 5, wherein the decrystallization agent is present in the interpenetrating network structure. The method for producing a multi-structure balloon according to claim 6, wherein the amorphizing agent is a phenol compound. The method for producing a multi-structure balloon according to claim 7, wherein the phenol compound is 1,3-dihydroxybenzene or t-butylhydroxyanisole. The bonding step includes
An application step of applying the decrystallization agent to the outer surface of the first tubular parison and / or the inner surface of the second tubular parison;
An insertion step of inserting the first tubular parison into the lumen of the second tubular parison and bringing it into close contact to form a double structure;
A blow molding step of simultaneously molding the first balloon and the second balloon by blow molding the double structure;
The method for producing a multi-structure balloon according to any one of claims 6 to 8, wherein: The bonding step includes
A first molding step of molding the second balloon by blow-molding the second tubular parison;
An application step of applying the decrystallization agent to the outer surface of the first tubular parison and / or the inner surface of the second balloon;
An insertion step of inserting the first tubular parison into the lumen of the second balloon;
Blow molding the inserted first tubular parison to mold the second balloon, and bringing the outer surface of the first tubular parison and the inner surface of the second balloon into close contact with each other, A second forming step of forming the second balloon into which the first balloon is telescopically inserted;
The method for producing a multi-structure balloon according to any one of claims 6 to 8, wherein:

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