WO2007065420A1

WO2007065420A1 - Catheter tube

Info

Publication number: WO2007065420A1
Application number: PCT/DE2006/002161
Authority: WO
Inventors: Jorge Calisse
Original assignee: B. Braun Melsungen Ag
Priority date: 2005-12-05
Filing date: 2006-12-05
Publication date: 2007-06-14
Also published as: DE112006003733A5; EP1957140A1

Abstract

The invention relates to catheter tubes for catheters such as angiographic catheters and dilatation catheters. Said catheter tubes are provided with an outer surface made of a plastic material and an inner surface which corresponds to the guide wire and is made of metal, metal alloy, glass, ceramics, or metal oxide.

Description

Catheter tube

description

The present invention relates to catheter tubes for catheters, wherein the catheter tubes have an outer surface made of a plastic or a polymeric material and an inner surface made of metal, metal alloy, glass, ceramic or metal oxide corresponding to the guide wire.

In medicine, high demands are placed on angiography catheters and dilatation catheters because, on the one hand, they have to be flexible so that they can be guided through tortuous vessels, and on the other hand they also have to have a kink stability in order to be able to be inserted well, which is called pushability referred to as. The stability in the axial direction is also in need of improvement. At increased pressure, the catheter tube expands along with the balloon. This can inadvertently treat or stretch healthy vessels. Furthermore, increased friction between the guidewire and the guiding tube must be avoided during the insertion process and, in the case of dilatation catheters, the guidewire volume must not collapse during dilation so that the mobility of the guidewire is not lost. Attempts have been made to solve these requirements by using a catheter tube. For example, European Patent EP 0 650 740 B1 describes the use of a catheter tube which is constructed in two layers and has an outer layer made of polyamide facing the catheter balloon and an inner layer made of polyethylene facing the guidewire. The catheter tube thus consists of a combination of two organic polymers.

This embodiment only insufficiently reduces the sliding friction between the catheter tube and the guide wire and furthermore does not have sufficient stability against collapse of the catheter tube volume when the catheter balloon is dilated. In addition, the buckling stability could be further improved in this embodiment.

As a further proposed solution, European Patent EP 0 608 853 B1 discloses the use of a catheter tube made of a superelastic metal, which from the inside, ie is coated with a synthetic resin on the surface facing the guide wire.

This solution also has problems with regard to undesirable friction between the synthetic resin surface and the guide wire.

There is therefore still a need for optimization of catheter tubes and the present invention has set itself the task of providing catheter tubes which avoid the described disadvantages of the designs of the prior art.

This object is achieved by the provision of a catheter tube according to claim 1. Further advantageous refinements, aspects and details of the invention result from the dependent claims, the description, the examples and the figures.

Surprisingly, it has been found that the disadvantages of the prior art can be overcome by producing the catheter tube from a polymer material which is flexible in order to also allow the catheter to curve and a hard material in the interior of the catheter tube which provides the friction minimized to the guidewire and prevents the catheter tube from collapsing when the balloon is dilated. In addition, the axial compression stability could be increased, whereby the insertion, i.e. the pushability is improved.

This means that such a construction is very flexible and at the same time also stable, in order to maintain the inner lumen of the catheter tube during the expansion of the balloon and to withstand the inward forces of the balloon which arise during the expansion.

This increased radial catheter tube stability significantly improves crimping of stents. The construction according to the invention can better withstand the pressure on the catheter tube which is exerted by the balloon when the stent is crimped, as a result of which a better fixing of the stent is made possible.

The catheter tube consists of common polymeric materials and, in the case of dilatation catheters, can also be made from the same polymer as the catheter balloon. Possible polymeric materials include in particular organic polymers such as polyacrylic acid, polyacrylates, polymethyl methacrylate, Polybutyl methacrylate, polyacrylamide, polyacrylonitriles, polyamides, polyetheramides, polyethylene amine, polyimides, polycarbonates, Polycarbourethane, polyvinyl ketones, polyvinyl halides, polyvinylidene halides, polyvinyl ethers, polyisobutylenes, polyvinyl aromatics, polyvinyl esters, polyvinylpyrrolidones, polyoxymethylenes, polytetramethylene oxide, polyethylene, polypropylene, polytetrafluoroethylene, polyurethanes, polyether silicone polyetherurethanes , Silicone polyurethanes, silicone polycarbonate urethanes, polyolefin elastomers, polyisobutylenes, EPDM rubbers, fluorosilicones, carboxymethylchitosans, polyaryl ether ether ketones, polyether ether ketones, polyethylene terephthalate, polyvalerates, carboxymethyl cellulose, cellulose, rayon, cellulose triacetyl ethyl acetate, cellulose triacetate ethylate cellulose , Ethyl vinyl acetate copolymers, polysulfones, epoxy resins, ABS resins, EPDM rubbers, silicones, polysiloxanes, polydimethylsiloxanes, polyvinyl halogens and copolymers , Cellulose ethers, cellulose triacetates. Chitosans, polyvalerolactones, poly-ε-decalactones, polylactonic acid, polyglycolic acid, polylactides, polyglycolides, copolymers of polylactides and polyglycolides, poly-ε-caprolactone, polyhydroxybutyric acid, polyhydroxybutyrates, polyhydroxyvalerates,

Polyhydroxybutyrate-co-valerate, poly (1,4-dioxane-2,3-dione), poly (1,3-dioxane-2-one), poly-para-dioxanones, polyanhydrides, polymaleic anhydrides, polyhydroxymethacrylates, fibrin, polycyanoacrylates, Polycaprolactone dimethyl acrylates, poly-ß-maleic acid polycaprolactone butyl acrylates,

Polyetherester multiblock polymers made from PEG and poly (butylene terephthalate), polypivotolactones, polyglycolic acid trimethyl carbonates, polycaprolactone glycolide, poly (γ-ethyl glutamate), poly (DTH-iminocarbonate), poly (DTE-co-DT-carbonate), poly (bisphenester A, imine , Polyglycolic acid trimethyl carbonates, polytrimethyl carbonates, polyiminocarbonates, poly (N-vinyl) pyrrolidone, polyvinyl alcohols, polyester amides, glycated polyesters, polyphosphoesters, polyphosphazenes, poly [(p-carboxyphenoxy) propane], polyhydroxypentanoic acid, polyanhydrides, polyethylene oxide, propylene oxide, polyethylene oxide propylene oxide Polyalkenoxalates, polyorthoesters, lipids, carrageenans, fibrinogen, starch, collagen, polyamino acids, zein, polyhydroxyalkanoates, pectic acid, actic acid, casein, carboxymethyl sulfate, albumin, hyaluronic acid, heparins, chondroitin sulfate, dextran, ß-cyclodextrin, gum, gum, gelatin, gelatin , Collagen-N-hydroxysuccinimide, lipids, phospholipids, modification NEN and copolymers and / or mixtures of the aforementioned substances. For example, polyamides are preferred.

In the case of dilatation catheters, the catheter tube is at least partially surrounded by the catheter balloon, which preferably surrounds the catheter tube in a sealing manner. Thus, the catheter balloon is preferably firmly and immovably connected to the catheter tube. The catheter tube is preferably welded or glued to the balloon end, preferably the distal end of the balloon. The catheter tube forms a longitudinal inner lumen for receiving the guide wire, the guide wire being movably mounted in this lumen. This creates frictional and torsional forces between the guide wire and the inner surface of the catheter tube. In order to reduce these frictional forces, guide wires are preferably coated with PTFE (polytetrafluoroethylene). In this case, PTFE should not be regarded as a plastic surface, but rather as a very stable and resistant material, has the function of a ceramic coating, which reduces abrasion and reduces sliding friction. The friction and torsional forces are absorbed in that the surface of the catheter tube corresponding to the guide wire is at least partially covered with a hard material such as a metal, a metal alloy, a glass, a ceramic, a metal oxide or a mixture of one or more of the aforementioned materials is lined. This results in a hard-hard pairing for the corresponding surface of the catheter tube and the guidewire, ideally two materials of the same hardness meet, whereby the friction between the catheter tube and the guidewire is significantly reduced. Since the bending stiffness is given by the outer layer or outer fiber or outer sheath, materials such as metals, alloys, glasses, ceramics or metal oxides can be used in the interior of the catheter tube, which serve as a corresponding surface for reducing friction. For example, Nitinol has a modulus of elasticity (E-module) of 41 - 75 GPa and stainless steel of 210 GPa, whereas the outer shell of the catheter tube consists of plastics or polymers with a significantly lower E-module, such as polyamide (PA 11) with an E- Module from 0.3 - 0.5 GPa or synthetic resin with a maximum of 1 GPa. Thus, the modulus of elasticity of the material of the corresponding inner surfaces of the catheter tube is greater than at least by a factor of 10, preferably a factor of 20, more preferably a factor of 40, more preferably a factor of 60, more preferably a factor of 80 and particularly preferably a factor of 100 the modulus of elasticity of the material of the outer tonsil or the outer sheath of the catheter tube.

The "corresponding surface" is the inner surface of the catheter tube, which is connected to the guide wire or to the surface of the Guide wire can come into contact. The contact surface is the inner surface of the catheter tube which actually comes into contact with the guide wire or with the surface of the guide wire at a specific point in time.

The corresponding surface of the catheter tube is thus the entirety of the contact surfaces. If the inner surface of the catheter tube is tubular, the corresponding surface corresponds to the entire inner surface. If, on the other hand, the inner surface of the catheter tube has elevations, regions can exist between the elevations which cannot come into contact with the guide wire, so that the corresponding surface makes up only part of the total surface.

The present invention is thus directed to catheter tubes which consist of a polymeric material and have an inner surface corresponding to the guide wire made of a metal, a metal alloy, a glass, a ceramic, a metal oxide or a mixture of at least two of the aforementioned materials. The hard material forming the corresponding surface is firmly bonded to the polymeric material.

As an embodiment of the present invention, catheter tubes are disclosed which consist of two layers, which are preferably arranged concentrically around one another. The outer layer consists of the polymeric material, e.g. a polyamide and the inner layer of the hard material. The aforementioned metals, metal alloys, glasses, ceramics, metal oxides or mixtures of these materials are referred to as “hard material”. The inner layer made of hard material can be in the form of a tube, a film or a coating and preferably has a wall thickness of 0.1 nm to 100 nm, preferably 5 to 100 nm.

If the inner layer consists of metal, such as a platinum-iridium foil, this additionally leads to an x-ray visibility of the catheter tube, which can further improve the accuracy of the stent placement and the crimp stability.

A further embodiment of the present invention is able to avoid the disadvantages of the prior art without having to accept a loss of stability of the inner lumen against collapse by placing the corresponding surface of the catheter tube on a partial area of the entire inner surface is reduced. This is done by creating surfaces that cannot come into contact with the guide wire.

This is achieved according to the invention by arranging balls, ridges, strips, bars, rails, rings, webs, spirals, one or more grids and / or one or more nets inside the catheter tube, which consist of the hard

Material exist and which form the corresponding surface. The entire corresponding surface is thus made up of the individual partial areas of the

Balls, ridges, strips, bars, rails, rings, bars, spirals, grids and / or nets together, which can come into contact with the guide wire.

Granules can also be used instead of balls. The particles of the granulate do not have a uniformly shaped surface, but are also approximately spherical.

These balls, granulate particles, elevations, strips, bars, rails, rings, webs, spirals, grids and / or nets are placed on the inside of the catheter tube on the polymeric material or embedded in the polymeric material, but in any case firmly with the polymeric material connected and / or embedded or embedded in the polymeric material.

Thus, raised structures are formed in the inner lumen of the catheter tube, which serve for contact with the guide wire and have a very low frictional resistance and yet are fixed to the catheter tube, i.e. are connected to the polymer of the catheter tube or the polymer of the inner part of the catheter tube in the case of multilayer catheter tubes, so that the raised structures are in the form of spheres, granulate particles, elevations, strips, bars, rails, rings, webs, spirals, grids and / or Cannot detach nets from the inner catheter tube.

Structures of this type can be formed by providing a core made of, for example, metal, ceramic and / or plastic, in which there are cutouts which contain the structures to be embedded in the catheter tube in the form of balls, granulate particles, elevations, strips, bars, rails, rings, Can accommodate webs, spirals, grids and / or nets. 6 shows, for example, a core designed as a ball holder with cutouts for receiving balls or essentially round particles. The individual balls as well as the other structures mentioned above can be mechanically, magnetically, by means of an adhesion promoter (for example temporary adhesive, grease, resin, wax etc.) and / or by Bottom of the recesses generated negative pressure are held on the core. The negative pressure at the bottom of the cutouts can be generated, for example, by channels running through the core, which lead to a vacuum pump. Instead of essentially round recesses as shown in FIG. 6, the core can of course also have oval, elongated, lattice-shaped, net-shaped, strip-shaped or spiral-shaped recesses and combinations of the aforementioned patterns. The structures to be inserted into the catheter tube protrude as far beyond the surface of the core as they are later to be introduced or embedded in the inner surface of the catheter tube. The catheter tube is then pulled over the core or formed around the core and the structures protruding from the core are embedded in the catheter tube, which is generally carried out at temperatures above 100 ^° C., preferably 150 ^° C.

Another possibility for producing the catheter tubes according to the invention is to mix balls or granulate particles with a polymer or polymer mixture and to form the catheter tubes from the mixture. The hard spherical structures are first completely embedded in the catheter tube and then exposed again by chemical and / or mechanical removal of the polymer material inside the catheter tube.

These balls, granulate particles, elevations, strips, bars, rails, rings, webs, spirals, grids and / or nets preferably rise in the direction of the inner axis of rotation of the catheter tube, so that there are surfaces between these elevations which are not in contact with the guide wire Can come into contact and are preferably made of the polymeric material from which the outer surface of the catheter tube facing the catheter balloon consists.

Metals, metal alloys, glass, ceramics and / or metal oxides can be considered as hard materials for these balls, elevations, strips, bars, rails, rings, webs, spirals, grids and / or nets.

Medicinal stainless steel, tantalum, titanium, cobalt, chromium, vanadium, tungsten, iridium, niobium, nickel, platinum, zirconium, zinc, iron, molybdenum, gold and magnesium can be mentioned as metals according to the invention. Alloys made of or with the following metals are suitable as alloys: medical stainless steel, tantalum, titanium, cobalt, chromium, vanadium, tungsten, iridium, niobium, nickel, platinum, zirconium, zinc, iron, molybdenum, gold and magnesium, and in particular nitinol, Titanium alloys, niobium alloys, titanium-aluminum-vanadium alloys (Ti ₆ AUV), titanium-aluminum-iron alloys (TiAls.sFe ^ s), titanium-aluminum-niobium alloys (TiAI ₇ Nb ₄ ), cobalt-nickel Alloys, cobalt-chrome-molybdenum alloys and cobalt-chrome alloys. The metal oxides which can be used according to the invention include, for example, aluminum oxide, titanium dioxide, zirconium oxide, niobium oxide and tantalum oxide. The metal oxides are also intended to include semimetal oxides.

Glasses made of silicon oxide, for example, are also suitable, and can also include various additives.

It is also preferred to use ceramics which comprise carbon, carbides, nitrides, silicates, phosphides and boron nitrides, such as, for example, diamond-like carbon, SiO ₂ , ZrO ₂ , Al ₂ O ₃ , titanium niobium oxynitride [(Ti ₁ Nb ) ON], titanium zirconium oxide [(Ti ₁ Zr) O ₃ ], tungsten carbide, chromium carbide, titanium carbide, silicon carbide, titanium niobium nitride (Ti-Nb-N) ₁ titanium calcium phosphide (Ti-Ca P) ₁ Cr-Al-N ₁ Ti-Al-N ₁ Cr-N, TiAIN-CrN, Ti-Al-C, Cr-C, TiAIC-CrC, Zr-Hf-N ₁ Ti-Hf-CN, Si -CN-Ti, Si-CN.

The hard inner corresponding surfaces made of metal, metal alloy, metal oxide or glass can preferably also be provided with a coating of a ceramic such as, for example, the carbides, nitrides, phosphides, bomitrides or diamond-like carbon mentioned herein. Through this

Coating increases the hardness of the surfaces again. An embodiment of a catheter tube according to the invention consists of a tube made of polyamide, which has thin wires, rails, strips or beams made of one of the hard materials described herein in its interior. These wires, rails, strips or bars are at least partially embedded in the polyamide and extend into the interior of the catheter tube. These wires, rails, strips or bars are preferably arranged along the longitudinal direction of the catheter tube and preferably have a thickness of less than 0.05 mm. At least three wires, rails, strips or bars are preferably used, more preferably at least five wires, rails, strips or bars are used. Another embodiment uses hard balls, cones, cylinders or other elevations, in particular round, rounded, oval or ellipsoidal elevations, which are preferably embedded in the polymer material up to half or more and which at least partially serve as a contact surface for the guide wire.

Another embodiment of the invention uses rings in the interior of the catheter tube, which rings are at least partially embedded in the polymeric material.

Yet another embodiment uses a spiral inserted into the interior of the catheter tube and further embodiments form the corresponding inner surface made of hard material through grids or nets lining the inner surface of the catheter tube or through at least one grille or at least one net.

Embodiments are of course also encompassed by the present invention, which combine different types of hard surfaces in the form of spheres, cones, cylinders, elevations, wires, rails, strips, bars, rings, webs, spirals, grids and / or networks. For example, a mesh made of, for example, a cobalt-chromium alloy can be located in the interior of a catheter tube made of plastic or polymer, metallic balls made of, for example, medical grade stainless steel being embedded in the gaps of the mesh. Another embodiment uses a thin film of nitinol with a thickness of 10 nm in the interior of the catheter tube, thin metal strips being placed or partially inserted onto this film or metallic or glass balls being pressed into this film and through this film, or one can be used Embed spiral made of hard material in the foil. There are no limits to the possible combinations of the various forms of hard materials mentioned here, as long as it is ensured that contact between the guidewire and the polymeric material for the outer sheath of the catheter tube is avoided. Not only different forms of corresponding inner surfaces can be combined with each other, but also different materials for such surfaces. Preferred embodiments use in particular different materials and also different shapes of corresponding surfaces in order to improve the properties of the catheter tube and thus of the whole Targeted control of the catheter. For example, the use of different materials along the longitudinal axis of the catheter tube as a corresponding surface is advantageous in order to design the bending strength accordingly. For example, progressive flexibility at the distal end, ie at the catheter tip, can be achieved through the use of metals (flexible), whereas reduced flexibility at the proximal end can be achieved through ceramics (rigid). In addition, the use of an X-ray-detectable film, for example a platinum-iridium film at the crimping point, as the corresponding surface is preferred in order to increase the X-ray visibility and to improve the crimping stability.

The catheter tubes according to the invention are used in catheters such as, for example, in dilatation catheters, angiography catheters, diagnostic catheters, overall-wire catheters, guiding catheters and interventional catheters.

Furthermore, the present invention is accordingly directed to catheters, dilatation catheters, angiography catheters, diagnostic catheters, overall-wire catheters, guiding catheters and interventional catheters and preferably to dilatation catheters which comprise a catheter tube according to the invention. Such catheters have a guide wire which is movably mounted in the catheter tube.

Dilatation catheters also have a catheter balloon which preferably tightly or sealingly encompasses the catheter tube at the distal end of the balloon. The surface of the catheter tube facing the catheter balloon is made of a polymeric material, but not of Teflon, and can also consist of the same material as the catheter balloon. The catheter tube and catheter balloon can be welded to one another in such a way that they form a unit. Furthermore, the catheter tube can be integrated in the catheter balloon in such a way that the inner surface or the inner part of the catheter balloon forms the catheter tube or is identical to the outer surface of the catheter tube. Furthermore, the catheter tube and the catheter balloon can be made in one piece, so that the inner cavity of the catheter balloon facing the guide wire forms the catheter tube. It is therefore not absolutely necessary for the catheter balloon and catheter tube to be two components of the catheter that can be separated from one another, but also to be formed from one piece.

The catheters according to the invention thus comprise the catheter tube made of at least two different materials which are firmly connected to one another and, in the case of dilatation catheters, a catheter balloon, the catheter tube being an inner one at least partially with the guide wire corresponding surface and an outer surface facing the catheter balloon, characterized in that the catheter tube and its outer surface consist of a polymeric material and the inner surface of the catheter tube corresponding to the guide wire made of a metal, a metal alloy, a glass , a ceramic and / or a metal oxide.

In other words, the present invention is directed to a catheter that has a catheter tube made of at least two different firmly bonded materials, a longitudinal lumen in the catheter tube for receiving a guide wire and, in the case of dilatation catheters, a catheter balloon with a proximal end and a distal end the catheter tube sealingly surrounding end, wherein the catheter tube comprises an inner surface at least partially corresponding to the guide wire and an outer surface, characterized in that the catheter tube and its outer surface consist of a polymeric material and the inner surface of the catheter tube corresponding to the guide wire consists of a metal, a metal alloy, a glass, a ceramic and / or a metal oxide.

In the case of dilatation catheters, the outer surface forms the surface facing the catheter balloon. As already stated, the catheter tube and catheter balloon can form a unit in the case of dilatation catheters or can also be formed from one piece.

The above-mentioned materials are of course preferably used as the polymeric material and as the hard material.

These embodiments according to the invention have good flexibility and manageability through tortuous vessels, are against collapse of the inner

Lumens protected, which receives the guidewire and at the same time reduce the friction between the guidewire and catheter tube to a minimum, because the

Guide wire can only interact with certain hard corresponding surfaces. The kink stability is comparable or better than in the conventional embodiments. Figure description

Fig. 1 shows a longitudinal view along vector A of a core with 3 slots and wires lying therein, which are detachably fixed at one end with cyanoacrylate.

FIG. 2 shows a top view (FIG. 2A) in the direction of the longitudinal axis of the core together with an enlarged section (FIG. 2B).

Fig. 3 shows a plan view in the direction of the longitudinal axis of the core according to the

Introducing the polyamide hose that covers the outer shell of the

Forms catheter tube.

Fig. 4 shows the fixation of the wires by means of thermal embedding in the

Polyamide.

FIG. 5 shows an embodiment of a catheter tube according to the invention with three wires forming the corresponding surfaces, FIG. 5A showing one

Top view along the longitudinal axis (vector A) of the catheter tube and Fig.

5B illustrates a perspective view of the interior of the catheter tube.

6 shows a core designed as a ball holder for holding 80 to 140

Balls preferably 90 to 130 balls per cm length of the core.

7 shows an embodiment according to the invention with balls as corresponding surfaces.

Fig. 8 shows the preparation of a film made of titanium-aluminum-niobium

Lining the inner corresponding surface of the catheter tube, wherein FIG. 8A shows a side view of the film and FIG. 8B shows the perforated film in perspective view and in side view, and FIG. 8C shows the perforated film along its longitudinal axis (vector A) after the perforated film rolled up into a tube and has been preferably welded along the weld with a laser.

Fig. 9 shows an inventive embodiment of a catheter tube (striped

Bars and dashed line), the striped bars representing the polyamide tube and the dashed line symbolizing the inner corresponding surface in the form of a ceramic-metal layer which is firmly connected to the polyamide tube and the catheter balloon is arranged around the outside of the catheter tube, the guide wire lying in the catheter tube is not shown. Examples

Example 1 :

Production of a catheter tube with metallic wires as the corresponding surface.

Materials:

Catheter tube material: Polyamide PA11

Number of wires: 3 or 6

Wire material: Nitinol

Diameter of the wires: 0.03 mm

Process: thermal embedding

Catheter balloon material: Polyamide PA12

Guide wire material: Stainless steel or Nitinol (PTFE coated)

The wires are punctual at one end! fixed with cyanoacrylate adhesive on a slotted core as shown in Figure 1. FIG. 2 shows a possible embodiment of a core with an enlargement, this core being able to accommodate three wires. Embodiments with four, five or even six wires can also be used. The core has at least the length of the catheter tube and is pushed into a tube made of PA11 (Fig. 3). The wires are firmly connected to the PA11 by means of thermal embedding as shown in FIG. For this purpose, the tube of PA11 with inserted core by a hot die at about 170 ⁰ C (melting point 175 ⁰ C) is drawn. The wires are thermally embedded in the PA11 tube. The core is then pulled out or turned out. 5 shows the obtained embodiment of a catheter tube according to the invention with three wires, which encompass the corresponding surfaces.

If instead of 3 wires 6 pieces are now to be used for the catheter tube according to the invention, the entire procedure can be repeated a second time, the core being introduced rotated by 60 ° compared to the first procedure, so that the individual wires are then at an angle to one another 60 ° to each other, or a core with 6 slots can also be used. Example 2:

Production of a catheter tube with metallic balls as corresponding ones

Surfaces. Materials:

Catheter tube material: Polyamide PA11

Number of balls per cross section: 3 pieces offset by 120 °

Ball diameter: 0.05 mm

Distance between the balls or the cross-sections: 0.3 mm

Ball material: strain-hardened stainless steel HRc 50 or ZrO ₂

Ball holder material: polyamide or polyethylene (PE)

Process: thermal embedding or injection molding

Catheter balloon material: Polyamide PA12

Guide wire material: Stainless steel or Nitinol (PTFE coated)

Embodiment A:

Via a ball holder (Fig. 6), i.e. A tube made of polyamide PA11 is formed into a core with recesses or recesses for partially receiving balls. The balls are held mechanically in the ball holder because their diameter is slightly larger than the diameter of the recesses in the ball holder. The recesses in the ball holder can be round or oval. The ball holder is preferably designed such that there are 3 balls in a cross-sectional area with an angle of 120 ° between the individual balls and the next cross-sectional area with a further three balls at a distance of 0.2 to 0.5 mm, preferably 0.3 mm follows and both planes are preferably rotated by 60 ° to each other. The third level is preferably rotated again by 60 ° to the second or 120 ° to the first level, so that the fourth level is again above the first. The balls are fixed in the PA11 by thermal embedding as described in Example 1. An inventive catheter tube with balls is obtained, which form the corresponding surfaces. The individual balls protrude as deeply into the interior of the catheter tube as they were previously sunk in the holes or recesses in the ball holder.

Embodiment B:

A hose made of polyamide PA11 is pulled over the aforementioned empty ball holder. There are no balls in the ball holder yet. The balls made of a) stainless steel HRc 50 or b) zirconium oxide are from the outside through the hose made of PA11 pressed into the holes or recesses of the ball holder. The balls protrude as far into the holes or recesses of the ball holder as they will later protrude into the interior of the catheter tube. The holes in the outer surface of the PA11 hose, where the balls were pressed through the hose, are closed again by a thermal process.

On the other hand, there is the possibility of closing the holes in the PA11 tube by applying a further polymer layer on the outside of the PA11 tube. This can be done, for example, by injection molding, in that the PA11 tube with a ball holder as the core is provided with a further polymeric layer in an injection molding device, this further polymeric layer also being PA11 or another polymer, preferably one of the polymers mentioned herein.

A third variant for closing the holes in the outer shell of the PA11 hose consists in pulling a further hose over the PA11 hose with embedded balls, which hose can also consist of PA11 or another polymer, in particular one of the polymers mentioned here. Both tubes lying one above the other are thermally welded or connected to one another at preferably 170 ^° C., and a catheter tube results from two layers, which can consist of the same or two different materials.

According to the aforementioned embodiments A and B, catheter tubes according to the invention with balls are obtained as corresponding surfaces (FIG. 7).

Example 3:

Production of a catheter tube with a metallic foil as the corresponding one

Surface. Materials:

Catheter tube material: Polyamide PA11

Material of the foil: titanium aluminum niobium

Wall thickness of the film: 3 nm

Process: extrusion

Catheter balloon material: Polyamide PA12

Guide wire material: Stainless steel or Nitinol (PTFE coated)

A film of titanium-aluminum-niobium with a thickness of 3 nm is perforated, deformed and shaped as shown in FIG. 8 before use in an extrusion machine then welded so that a tube results. The welding process is preferably carried out with a laser. Now the extrusion takes place, which creates a jacket made of polyamide PA11. An embodiment according to the invention is obtained with a metallic inner film as the corresponding surface, which is firmly connected to the outer shell made of PA11.

Example 4:

Production of a catheter tube with ceramic spherical particles made of silicon dioxide as corresponding surfaces.

Materials:

Catheter tube material: Polyamide PA11

Amount of SiO ₂ particles: 10% by weight based on the catheter tube

Particle diameter: 0.010 mm (10 μm)

Particle material: SiO ₂

Core material: stainless steel

Procedure: mixing

Catheter balloon material: Polyamide PA12

Guide wire material: stainless steel

The essentially spherical silicon particles with an average particle size of 10 μm are added in an amount of 10% by weight to the polyamide PA11, from which the catheter tube is then formed. The polymer material in the interior of the catheter tube is removed by mechanical abrasion, whereby the silicon particles are exposed, which then form the corresponding surface for the guide wire.

Example 5:

Production of a catheter tube with a metallic spiral as the corresponding surface. Materials:

Catheter tube material: three layers, high-density polyethylene inside, low-density polyethylene in the middle, polyamide outside Number of spirals: 1

Material of the spiral: cobalt chrome Wire diameter: 0.025 mm

Process: thermal embedding

Catheter balloon material: Polyamide PA12

Guide wire material: Stainless steel coated with PTFE

A stainless steel core with a spiral recess is provided. A spiral of cobalt chrome is wrapped around the core and in the recess. The distance between the windings, ie the feed per winding is 0.2 mm. The three-layer catheter tube is now guided over the longitudinal axis of the core. By thermal embedding at 160-180 ⁰ C, the coil is embedded in the high density polyethylene. The core is unscrewed and a catheter tube with a spiral-like corresponding surface is obtained.

Example 6:

Experiment 5 is repeated, this time a polyamide catheter tube and one

Spiral made of titanium is used.

Example 7:

Determination of the frictional resistance of the catheter tubes according to the invention in

Compared to catheter tubes without the inner hard corresponding surface. A catheter tube according to the invention and two controls (catheter tube without an internal raised structure) are clamped vertically one after the other in a device.

The one catheter tube serving as control (control I) was previously thermally treated in the same way as the catheter tube according to the invention. For this purpose, the catheter tube serving as a control was also clamped onto a core, which, however, had no recesses and was thermally treated at the same time as the catheter tube according to the invention, which was clamped onto a core with recesses and structures to be transferred. The second catheter tube serving as control (control II) remains untreated.

One after the other, the catheter tubes of the same length were clamped vertically into the measuring device and a guide wire made of stainless steel was slowly inserted completely into the catheter tube from above. It started with the catheter tube according to the invention according to Example 1 with 6 wires made of Nitinol. This was followed by the catheter tube according to the invention with silicon particles according to Example 4. As controls, appropriate catheter tubes without an internal structure were measured, as described above. The frictional resistance was now measured when pulling out the guide wire.

The standard deviation for the tests was 0.22 N to 0.26 Newton. A frictional resistance of 0.68 N was determined for the catheter tube according to the invention according to Example 1 and 0.74 N for the catheter tube according to the invention according to Example 4. The controls, however, delivered

Frictional resistances from 1.47 N to 1.56 N.

A percentage improvement with regard to the frictional resistance can be obtained if the absolute values are compared to one another as shown in the following table.

Reduction of friction resistance:

Claims

1. Catheter tube with a longitudinal lumen for receiving a guidewire for a catheter, the catheter tube consisting of at least one polymeric material and an inner surface corresponding to the guidewire made of a metal, a metal alloy, a glass, a ceramic, a metal oxide or one Mixture of at least two of the aforementioned materials.

2. Catheter tube according to claim 1, wherein the catheter tube consists of two firmly connected layers and the outer layer of a polymeric material and the inner layer facing the guide wire of a metal, a metal alloy, a glass, a ceramic, a metal oxide or a mixture consists of at least two of the aforementioned materials.

3. The catheter tube of claim 1, wherein the inner surface corresponding to the guidewire is only a portion of the total inner surface.

4. The catheter tube according to claim 3, wherein the inner surface corresponding to the guide wire is formed from a sum of individual surfaces corresponding to the guide wire.

5. Catheter tube according to claim 1, 3 or 4, wherein the inner surface corresponding to the guide wire in the form of spheres, granulate particles, elevations, strips, bars, rails, rings, webs, spirals, one or more grids and / or one or more Networks is designed.

6. The catheter tube according to claim 5, wherein the spheres, granulate particles, elevations, strips, bars, rails, rings, webs, spirals, grids and / or nets forming the corresponding inner surface with the guide wire are at least partially embedded or embedded in the polymeric material .

7. The catheter tube according to claim 5 or 6, wherein the spheres, granulate particles, elevations, strips, bars, rails, rings, webs, spirals, grids and / or nets extending into the interior of the catheter tube form the inner surface corresponding to the guide wire.

8. Catheter tube according to one of the preceding claims, wherein the inner surface corresponding to the guide wire is coated with a ceramic.

9. Catheter tube according to one of the preceding claims, wherein the inner surface corresponding to the guide wire made of metal, metal alloy, glass, ceramic and / or metal oxide comprises the following materials: medical stainless steel, tantalum, titanium, cobalt, chromium, vanadium, tungsten, molybdenum, Gold, nitinol, magnesium, titanium alloys,

Niobium alloys, cobalt-chromium alloys, aluminum oxide, silicon oxide, carbide, diamond-like carbon, nitride, phosphide, boron nitride, titanium-niobium nitride (Ti-Nb-N), titanium-calcium phosphide (Ti-Ca-P ), Cr-Al-N, Ti-Al-N, Cr-N, TiAIN-CrN, Ti-Al-C, Cr-C, TiAIC-CrC, Zr-Hf-N, Ti-Hf-CN, Si CN-Ti, Si-CN.

10. Catheter tube according to one of the preceding claims, wherein the polymeric material is selected from the group comprising: polyacrylic acid, polyacrylates, polymethyl methacrylate, polybutyl methacrylate, polyacrylamide, polyacrylonitriles, polyamides, polyether amides, polyethylene amine, polyimides, polycarbonates, polycarbourethanes, polyvinyl ketones, polyvinyl halides,

Polyvinylidene halides, polyvinyl ethers, polyisobutylenes, polyvinyl aromatics, polyvinyl esters, polyvinyl pyrollidones, polyoxymethylenes, polytetramethylene oxide, polyethylene, polypropylene, polytetrafluoroethylene, polyurethanes,

Polyether urethanes silicone polyether urethanes, silicone polyurethanes, silicone polycarbonate urethanes, polyolefin elastomers, polyisobutylenes, EPDM

Gums, fluorosilicones, carboxymethylchitosans, polyaryl ether ether ketones, polyether ether ketones, polyethylene terephthalate, polyvalerates,

Carboxymethyl cellulose, cellulose, rayon, rayon triacetates, cellulose nitrates, cellulose acetates, hydroxyethyl cellulose, cellulose butyrates, cellulose acetate butyrates, ethyl vinyl acetate copolymers, polysulfones, epoxy resins,

ABS resins, EPDM rubbers, silicones, polysiloxanes, polydimethylsiloxanes, polyvinyl halogens and copolymers, cellulose ethers, cellulose triacetates. Chitosans, polyvalerolactones, poly-ε-decalactone, polylactonic acid, polyglycolic acid, polylactides, polyglycolides, copolymers of polylactides and polyglycolides, poly-ε-caprolactone, polyhydroxybutyric acid,

Polyhydroxybutyrates, polyhydroxyvalerates, polyhydroxybutyrates-co-valerates, poly (1,4-dioxane-2,3-diones), poly (1,3-dioxane-2-ones), poly-para-dioxanones, polyanhydrides, polymaleic anhydrides, polyhydroxymethacrylates, Fibrin, polycyanoacrylates, polycaprolactone dimethylacrylates, poly-ß-maleic acid Polycaprolactone butyl acrylates, polyetherester multi-block polymers made from PEG and poly (butylene terephthalate), polypivotolactones, polyglycolic acid trimethyl carbonates, polycaprolactone glycolide, poly (γ-ethyl glutamate), poly (DTH-iminocarbonate), poly (DTE-co-im-bis-carbonate), poly (DTE-co-im-bis-carbonate) , Polyorthoesters, polyglycolic acid trimethyl carbonates, polytrimethyl carbonates

Polyiminocarbonates, poly (N-vinyl) pyrrolidone, polyvinyl alcohols,

Polyester amides, glycolated polyesters, polyphosphoesters, polyphosphazenes, poly [(p-carboxyphenoxy) propane], polyhydroxypentanoic acid, polyanhydrides, polyethylene oxide propylene oxide, polyurethanes, polyether esters, polyethylene oxide, polyalkenoxalates, polyorthoesters, lipids, carrageenans, fibrinogen, starch,

Collagen, polyamino acids, zein, polyhydroxyalkanoates, pectic acid, actic acid, casein, carboxymethyl sulfate, albumin, hyaluronic acid, heparins, chondroitin sulfate, dextran, ß-cyclodextrins, gum arabic, guar, gelatin, collagen, collagen-N-hydroxysuccinolipid, lipide and copolymers and / or mixtures of the aforementioned substances.

11. Catheters comprise the catheter tube according to one of claims 1-10 as well as a catheter balloon connected to the catheter tube and a guide wire which can be movably supported in the catheter tube.