DE10134008A1 - Fluoropolymer tubes, for use e.g. as catheters, comprising ring-form X-ray-distinguishable markings, e.g. of titanium dioxide, with an X-ray-distinguishable coating - Google Patents

Abstract

A tube with a wall (102) of a fluoropolymer (especially polytetrafluoroethylene (PTFE), perfluoroalkoxy polymer (PFA) or fluorinated ethylene/propylene (FEP)) comprises X-ray-distinguishable markings which are of ring-form and are covered by an X-ray-distinguishable coating (110).

Description

The present invention relates to a hose, the one a fluoropolymer, in particular polytetrafluoroethylene (PTFE), a perfluoroalkoxy polymer (PFA) and / or a fluorinated one Ethylene propylene (FEP), comprehensive wall and one radiopaque marking includes.

The present invention further relates to a method for Marking a hose, the wall of which is a fluoropolymer, especially polytetrafluoroethylene.

The term "polytetrafluoroethylene" includes within the scope of this Description and the appended claims other than pure Polytetrafluoroethylene (PTFE) also modified Polytetrafluoroethylene, a polytetrafluoroethylene compound or a modified polytetrafluoroethylene compound.

Among them is a "modified polytetrafluoroethylene" to understand a PTFE-like substance in which the Molecular structure of the PTFE has been chemically modified that the fluorine atoms of PTFE partly due to substituents are replaced.

Such a modified PTFE is for example under the Designation 62N known and from the company Du Pont too Respectively.

Under a "polytetrafluoroethylene compound" is a mixture made of PTFE and at least one organic or inorganic Understand filler. As such fillers come in particular glass fibers, carbon fibers, coal, graphite, bronze or organic fillers, especially high temperature resistant Thermoplastics and thermosetting plastics.

Accordingly, under a "modified Polytetrafluoroethylene compound "to understand a mixture, which a modified polytetrafluoroethylene, for example 62N, and at least one organic or inorganic filler includes.

Show hoses with a wall made of polytetrafluoroethylene high chemical resistance, good Temperature resistance as well as anti-adhesive properties, which is why Tubing in numerous applications in chemical, electrical and mechanical industry as well as in the Medical technology are used.

In particular, it is known to make hoses Polytetrafluoroethylene with colored markings, for example with Ring markings, in medical technology as catheter tubes, Papillotomes, or as tubes for endoscopy use.

The color markings serve both different To distinguish hoses from each other as well identified hose in a desired location position.

Color markings can be used for identification and Positioning a hose can only be used if the hose can be observed in visible light is. Especially in medical technology, but also with others Applications, it happens, however, that the hose only in X-ray light can be viewed so that on the tube attached color markings are not recognizable.

In order to have a radiopaque mark on the To get hose, it is already known to be metallic Press marking sleeves onto a PTFE tube or press into a PTFE tube.

However, this has the disadvantage that the Outside diameter of the relevant hose on the Marking point by the pressed sleeve increases or that the inside diameter of the hose through the inside of the hose Pressed-in metallic sleeve reduced.

Increasing the outside diameter has the disadvantage with the fact that the insertion of the hose into a Through channel is difficult. In addition, the hose with the End faces of the metal sleeve used on an obstacle get stuck.

If the metallic sleeve is pressed into the hose, so will carry out probes, light guides and other Objects hindered by the interior of the hose.

Another disadvantage of using metal sleeves is that dirt and bacteria on the metal sleeves can accumulate what a cleaning or even sterilization of the hose difficult.

Another disadvantage is that the flexibility of the PTFE hose in the area of the metal sleeve is reduced.

Finally, it is also difficult to put the metal sleeve on or non-slip in the comparatively soft PTFE tube Fasten.

The present invention is therefore based on the object to create a hose of the type mentioned at the beginning, which by the radiopaque mark is identifiable and / or positionable without the advantages of a Lose tubing made of fluoropolymer material.

This task is performed with a hose with the characteristics of a Preamble of claim 1 solved according to the invention in that that the marking comprises an X-ray contrast coating, which contains a radiopaque material.

Under an X-ray contrast material is a To understand material which is a significantly higher Has X-ray absorptivity than the material the wall of the hose, so that marked points of the X-ray tube clearly from unmarked Places of the hose are distinguishable.

The inventive concept, in which the wall of the Hose directly or indirectly with a coating is provided, which contains a radiopaque material, are used by using a metallic sleeve separate part associated disadvantages avoided while the Advantages of the tube made of the fluoropolymer material, in particular sterilizability, flexibility and Biocompatibility, preserved.

It is already known that the material from which a PTFE Tube is extruded, a radiopaque contrast Add material, such as bismuth carbonate, to the Overall wall of the hose increased To give absorption so that the tube in the X-ray image of its surroundings can be distinguished.

Because here the hose in its entirety with the X-ray contrast material and no marking is not possible with such a hose, the tube due to the radiopaque material to be distinguished from other hoses and / or the hose to position in a desired position.

To ensure that the marked provided areas of the hose sufficient of the not marked areas of the tube in the X-ray image distinguish, it is advantageous if the x-ray contrast coating at least about 10% by weight radiopaque Contains material.

To be an abrasion resistant and easy to manufacture To get x-ray contrast coating, it is advantageous if the X-ray contrast coating at most about 40% by weight, preferably at most about 30% by weight, contains radiopaque material.

To keep the outer diameter of the hose as small as possible hold and the flexibility of the hose not too impair, it is preferably provided that the marking a total thickness of at most about 50 µm, preferably of at most about 20 µm.

Below the total thickness of the marking is when the Marking only includes the x-ray contrast coating, the thickness to understand the X-ray contrast coating. Includes the Marking in addition to the X-ray contrast coating Layers, the total thickness corresponds to the sum of the thicknesses of the superimposed layers.

The x-ray contrast coating can be formed by that contains the X-ray contrast material Primary material applied to the hose in a suitable manner, for example sprayed on, printed on or brushed on and then the primary material on the wall of the Hose is fixed.

In a preferred embodiment of the invention provided that the x-ray contrast coating by spraying one containing the X-ray contrast material Suspension is formed.

In order to be particularly firm with the fluoropolymer material of the To get the hose-connected, abrasion-resistant marking, can be provided that the X-ray contrast coating a polytetrafluoroethylene (PTFE), PFA or FEP wetting Suspension is formed.

It is particularly favorable if the X-ray contrast coating made of fluorinated ethylene propylene (FEP) containing suspension is formed.

Around the hose even when observed in visible light To be able to identify and / or position it is from Advantage if the marking is a color marking layer comprises which contains at least one pigment.

To avoid the color of the pigment from the addition of the radiopaque material has faded preferably provided that the color marking layer one of the X-ray contrast coating different layer of the Mark is.

In this case, the pigment and the X-ray contrast material in different work steps on the Hose applied, which is the processing of the pigment or the material containing X-ray contrast Simplified materials.

Due to an excessively high proportion of X-ray contrast These materials are namely material and pigment heavily thickened and are then difficult to process, especially difficult to spray on.

To affect the detection of the Color marking layer due to a bleaching or light-absorbing effect to exclude the X-ray contrast coating, it is favorable if the color marking layer over the X-ray contrast coating is arranged.

To avoid X-ray contrast material from the X-ray contrast coating out in the vicinity of the Hose comes in a preferred embodiment of the hose according to the invention provided that the Marking comprises an outer protective layer which is essentially contains no X-ray contrast material.

To the perception of a possibly existing It is advantageous not to impair the color marking layer provided that the outer protective layer essentially is transparent.

Under "transparency" there is a permeability to light to understand in the visible range of the spectrum.

As particularly suitable for the X-ray contrast coating X-ray contrast materials have bismuth carbonate, Proved barium sulfate and / or titanium dioxide.

To mark the hose not only identify, but also in a desired location along its Longitudinal axis and / or in a desired angular position to be able to position with respect to its longitudinal axis convenient if the marker is less than the entire Outer surface of the hose covered.

Basically, the marking can have any shape exhibit.

In particular, it can be provided that the marking is annular.

Furthermore, the preferred embodiment of the invention provided that the hose has several marks that are spaced from each other.

The markings can be along the longitudinal direction and / or along the circumferential direction of the hose from each other be spaced.

To different markings of the same hose from each other To be able to distinguish, it can be provided that the Markings with regard to their geometric shape differentiate from each other.

For example, it can be provided that the markings as Rings of different widths, d. H. different Expansion along the longitudinal direction of the hose, formed are.

It can also be provided that the markings differ from each other in that they consist of a different number of sub-marks composed are.

For example, a marker can be one, two, three or include even more rings than partial marks.

It is also possible that at least two of the Markings with regard to their absorbency for Differentiate between X-rays.

This leads to the markings in the x-ray image in different gray values appear and therefore differ from each other are distinguishable.

The present invention has another object based on a method for marking a hose of the to create the type mentioned above, which is a flawless Identification and / or positioning of the hose enables while taking advantage of a hose Polytetrafluoroethylene (PTFE), PFA or FEP.

This task is carried out in a process with the characteristics of The preamble of claim 18 by the following Process step solved:

Applying a coating which a contains radiopaque material, directly or indirectly on the wall of the hose.

In particular, it can be provided that the X-ray contrast coating by spraying on the radiopaque one Material containing suspension is applied.

In a preferred embodiment of the invention The method provides for several coatings of at least one of which is an X-ray contrast material contains, one above the other on the wall of the hose be applied.

For example, it can be provided that one of the Coatings the X-ray contrast coating is while a second coating is a color marking layer and one third, outermost layer an outer protective layer of the Mark forms.

A particularly intimate and abrasion-resistant connection of the majority of coatings is achieved when at least one of the Coatings on an underlying coating is applied before the underlying coating is fixed has been.

To prevent that when using the marked X-ray contrast material from the X-ray contrast coating of the hose in the vicinity of the hose arrives, it can be provided that the farthest outside horizontal coating essentially none contains radiopaque material and thus as a seal of the Marking serves.

Other features and advantages of the invention are the subject the following description and graphic representation of embodiments.

The drawings show:

Figure 1 is a side view of a portion of a hose with a wall made of PTFE, PFA or FEP and several markings.

FIG. 2 shows a schematic longitudinal section through the wall of the hose from FIG. 1 and a marking arranged thereon;

Fig. 3 is a schematic cross-section through the wall of the hose of Figure 2 with the marker disposed thereon, taken along line 3-3 in FIG. 2.

Figure 4 is a side view of a portion of a second embodiment of a hose with a mark extending in the longitudinal direction of the hose. and

Fig. 5 is a side view of a portion of a third embodiment of a hose with a marking arranged on the wall of the hose, which comprises alphanumeric characters.

The same or functionally equivalent elements are in all Figures with the same reference numerals.

A in FIGS. 1 to 3 shown as a whole by 100, designated hose comprises a flexible, hollow cylindrical wall 102 which encloses a cylindrical inner space 104 of the tube and extending along a longitudinal direction 106 extends the hose.

The wall 102 of the tube 100 is formed, for example by a paste extrusion process, from polytetrafluoroethylene (PTFE), from modified polytetrafluoroethylene, from a polytetrafluoroethylene compound, or from a modified polytetrafluoroethylene compound or, for example by a thermoplastic extrusion process, from PFA or from FEP educated.

The hose 100 is provided with a plurality of markings 108 which surround the wall 102 of the hose 100 in an annular manner and are spaced apart from one another in the longitudinal direction 106 .

The markings 108 differ in their color; for example, a first marking 108 a, which surrounds the wall 102 in a ring, is colored black in a manner to be described in more detail below.

Further annular markings 108 b, 108 c, 108 d following the first black marking 108 a, which are spaced apart from one another along the longitudinal direction 106 of the hose 100 , are colored green, yellow or red, for example.

The red marking 108 d is followed by a further black colored marking 108 e, which is designed as a double marking and comprises two ring-shaped, black colored partial markings.

The different colors enable the markings 108 to be differentiated if it is possible to observe them with visible light, for example using a video camera.

In order to make the markings 108 distinguishable from one another even when observed with X-ray light, the markings 108 are provided with different X-ray absorption capacities in a manner described in more detail below.

As shown in FIGS. 2 and 3 by way of example for the green marking 108 b, each of the markings 108 comprises three layers one above the other on the outside of the wall 102 of the tube 100 , namely an X-ray contrast layer 110 arranged directly on the outside of the wall 102 arranged on the X-ray contrast layer 110 color layer 112, and a marking disposed on the marking color layer 112 outer protective layer 114th

The x-ray contrast layer 110 is produced by spraying the outside of the wall 102 of the tube 100 with an aqueous suspension.

• - 100 Gewichtsteile einer wäßrigen Fluorkunststoff-Emulsion, die ungefähr 30 bis ungefähr 60 Gewichts-% in Wasser dispergiertes PTFE oder FEP (fluoriertes Ethylen- Propylen) als Bindemittel, bis zu ungefähr 10 Gewichts-% Urethanpolymer und geringe Mengen eines Benetzungsmittels (beispielsweise Alkohole oder Ammoniak) enthält; und
• - ungefähr 10 bis ungefähr 40 Gewichtsteile eines röntgenkontrastfähigen Füllstoffs (beispielsweise Bariumsulfat, Wismutkarbonat oder Titandioxid).

This aqueous suspension has, for example, the following composition:

• - 100 parts by weight of an aqueous fluoroplastic emulsion containing about 30 to about 60% by weight water-dispersed PTFE or FEP (fluorinated ethylene propylene) as a binder, up to about 10% by weight urethane polymer and small amounts of a wetting agent (e.g. alcohols or Ammonia) contains; and
• about 10 to about 40 parts by weight of a radiopaque filler (for example barium sulfate, bismuth carbonate or titanium dioxide).

• - 100 Gewichtsteile einer wäßrigen FEP-Emulsion, die 55 Gewichts-% FEP enthält; und
• - 20 Gewichtsteile Bariumsulfat.

An aqueous suspension with the following composition is particularly preferred for producing the X-ray contrast layer 110 :

• 100 parts by weight of an aqueous FEP emulsion containing 55% by weight of FEP; and
• - 20 parts by weight of barium sulfate.

Such an FEP dispersion wets the surface of the wall 102 made of PTFE, so that a reliable, abrasion-resistant hold of the x-ray contrast layer on the wall 102 of the tube 100 is ensured after the stoving of the x-ray contrast layer 110 .

The X-ray absorption capacity of the X-ray contrast layer 110 can be influenced by varying the proportion of the X-ray-contrasting filler.

The higher the weight proportion of the radiopaque one Filler is and the higher the specific X-ray absorption capacity of the filler, the darker it appears corresponding marking in the x-ray image.

The color marking layer 112 following the X-ray contrast layer is produced by spraying an aqueous suspension onto the X-ray contrast layer 110 which is still “wet”, ie not yet fixed by baking.

• - 100 Gewichtsteile einer wäßrigen Fluokunststoff-Emulsion, die ungefähr 30 bis 60 Gewichts-% in Wasser dispergiertes PTFE oder FEP als Bindemittel, bis zu ungefähr 10 Gewichts-% Urethanpolymer und geringe Mengen eines Benetzungsmittels (beispielsweise Alkohole oder Ammoniak) enthält; und
• - ungefähr 2 bis ungefähr 30 Gewichtsteile eines hitze- und lichtbeständigen Farbpigments.

The suspension used to produce the color marking layer 112 can have the following composition, for example:

• - 100 parts by weight of an aqueous fluoroplastic emulsion containing about 30 to 60% by weight of water-dispersed PTFE or FEP as a binder, up to about 10% by weight of urethane polymer and small amounts of a wetting agent (e.g. alcohols or ammonia); and
• about 2 to about 30 parts by weight of a heat and light-resistant color pigment.

• - 100 Gewichtsteile einer wäßrigen FEP-Emulsion, die 45 Gewichts-% FEP und 2 Gewichts-% Urethanpolymer enthält; und
• - 16 Gewichtsteile eines (beispielsweise grünen) Pigments. Durch die Art des zugesetzten Pigments wird die Farbe der Markierung 108 gewählt.

In a preferred embodiment of the color marking layer 112 , it is produced from an aqueous suspension having the following composition:

• 100 parts by weight of an aqueous FEP emulsion containing 45% by weight of FEP and 2% by weight of urethane polymer; and
• - 16 parts by weight of a (for example green) pigment. The color of the marking 108 is selected by the type of pigment added.

Since the suspension used for producing the color marking layer 112 as PTFE, PFA or FEP-wetting as the suspension used for the X-ray contrast layer 110, a good abrasion-resistant retention of the color marking layer is ensured 112 on the X-ray contrast layer 110 after baking.

The outer protective layer 114 is produced by spraying an aqueous emulsion onto the color marking layer 112 which is still "wet", ie not yet hardened by baking.

• - ungefähr 30 bis ungefähr 60 Gewichts-% PTFE oder FEP als Bindemittel;
• - bis zu ungefähr 10 Gewichts-% Urethanpolymer;
• - geringe Mengen eines Benetzungsmittels (beispielsweise Alkohole oder Ammoniak);
• - Rest Wasser.

The aqueous emulsion used to produce the outer protective layer 114 has, for example, the following composition:

• about 30 to about 60% by weight of PTFE or FEP as a binder;
• - up to about 10% by weight urethane polymer;
• - small amounts of a wetting agent (e.g. alcohols or ammonia);
• - rest of water.

In a preferred embodiment of the outer protective layer 114 , the same is produced from an aqueous FEP emulsion with an FEP content of 55% by weight.

After the outer protective layer 114 has been sprayed on , the three layers of the marking 108 are cured by baking, ie by increasing the temperature to, for example, approximately 360 ° C., and fixed on the wall 102 of the hose 100 .

This heating can be carried out, for example, by applying heated air to the marking 108 .

In particular, it is possible to supply the heated air through a stationary nozzle, the hose 100 being rotated about its longitudinal axis.

Since the tube is locally heated to a temperature that is above the melting temperature of FEP (approximately 290 ° C) and PFA (approximately 310 ° C) and above the softening temperature of PTFE (approximately 330 ° C), burn-in occurs intimate connection between the wall 102 of the hose 100 and the layers of the marking 108 arranged thereon.

The layers 110 , 112 and 114 thus formed are absolutely abrasion-resistant, sterilizable and biocompatible.

The inner diameter of the hose is not reduced by the production of the marking 108 , and the outer diameter of the hose is only slightly increased by the application of the marking 108 , since the layers are comparatively thin in relation to the thickness of the wall 102 .

The total thickness of the layers of the marking 108 is preferably at most approximately 50 μm.

Due to the small thickness of the marking 108 , the flexibility of the hose 100 is not impaired by the application of the marking 108 .

The individual markings 108 a to 108 e can be made in succession or simultaneously on the wall 102 of the hose 100 in the manner described above.

The shape of the markings 108 is not limited to the ring shape, but can take any shape.

The second embodiment of a hose 100 shown in FIG. 4 is provided on the outside of the wall 102 with a marking 108 , which does not surround the wall 102 in an annular manner, but rather extends linearly in the longitudinal direction 106 of the hose 100 .

The marking 108 can extend over the entire length of the hose 100 or only over a partial section of the hose.

Such a marking 108 makes it possible in particular to determine the angular position of the hose 100 with respect to its longitudinal axis or to set a desired angular position of the hose. This is of particular interest if the interior of the hose 100 is not rotationally symmetrical.

In a third embodiment of a hose 100 , shown in FIG. 5, the marking 108 arranged on the outside of the wall 102 comprises a sequence of alphanumeric characters.

With such alphanumeric characters it is also possible identify the hose and / or lengthways and / or in the circumferential direction in the desired manner position.

The markings can also be any other in the Drawings not shown form; for example can be helical markings or markings in shape of barcodes, company logos or the like.

The x-ray contrast layer 110 of each marking 108 makes it possible to identify the relevant marking 108 in the x-ray image.

The color marking layer 112 of each marking 108 makes it possible to identify the marking in question when observing with visible light, for example by means of a video camera.

The colorless, transparent outer protective layer 114 prevents the X-ray contrast material from the X-ray contrast layer 110 and / or the pigments from the color marking layer 112 from escaping into the vicinity of the tube.

Claims (22)

1. tube, comprising a wall ( 102 ) which comprises a fluoropolymer, in particular polytetrafluoroethylene (PTFE), a perfluoroalkoxy polymer (PFA) and / or a fluorinated ethylene-propylene (FEP), and an X-ray-contrastable marking ( 108 ), characterized in that the marking ( 108 ) comprises an X-ray contrast coating ( 110 ) which contains an X-ray contrast material. 2. Hose according to claim 1, characterized in that the X-ray contrast coating ( 110 ) contains at least approximately 10% by weight of X-ray contrast material. 3. Hose according to one of claims 1 or 2, characterized in that the X-ray contrast coating ( 110 ) contains at most approximately 40% by weight, preferably at most approximately 30% by weight, of X-ray contrast material. 4. Hose according to one of claims 1 to 3, characterized in that the marking ( 108 ) has a total thickness of at most about 50 microns, preferably of at most about 20 microns. 5. Hose according to one of claims 1 to 4, characterized in that the X-ray contrast coating ( 110 ) is formed by spraying a suspension containing the X-ray contrast material. 6. Hose according to one of claims 1 to 5, characterized in that the x-ray contrast coating ( 110 ) is formed from a PTFE, PFA or FEP wetting suspension. 7. Hose according to one of claims 1 to 6, characterized in that the X-ray contrast coating ( 110 ) is formed from a suspension containing fluorinated ethylene-propylene. 8. Hose according to one of claims 1 to 7, characterized in that the marking ( 108 ) comprises a color marking layer ( 112 ) which contains at least one pigment. 9. Hose according to claim 8, characterized in that the color marking layer ( 112 ) is a different from the X-ray contrast coating ( 110 ) layer of the marking. 10. Hose according to claim 9, characterized in that the color marking layer ( 112 ) over the X-ray contrast coating ( 110 ) is arranged. 11. Hose according to one of claims 1 to 10, characterized in that the marking ( 108 ) comprises an outer protective layer ( 114 ) which contains essentially no X-ray contrast material. 12. Hose according to claim 11, characterized in that the outer protective layer ( 114 ) is substantially transparent. 13. Hose according to one of claims 1 to 12, characterized characterized in that the X-ray contrast material Bismuth carbonate, barium sulfate and / or titanium dioxide includes. 14. Hose according to one of claims 1 to 13, characterized in that the marking ( 108 ) covers less than the entire outer surface of the hose ( 100 ). 15. Hose according to one of claims 1 to 14, characterized in that the marking ( 108 ) is annular. 16. Hose according to one of claims 1 to 15, characterized in that the hose ( 100 ) has a plurality of markings ( 108 ) which are spaced apart. 17. Hose according to claim 16, characterized in that at least two of the markings ( 108 ) differ from one another in terms of their absorption capacity for X-radiation. 18. A method for marking a hose ( 100 ), the wall ( 102 ) of which comprises a fluoropolymer, in particular polytetrafluoroethylene (PTFE), a perfluoroalkoxy polymer (PFA) and / or a fluorinated ethylene propylene (FEP), characterized by the following process step : Applying a coating, which contains an X-ray contrast material, directly or indirectly to the wall ( 102 ) of the tube. 19. The method according to claim 18, characterized in that the X-ray contrast coating ( 110 ) is applied by spraying a suspension containing the X-ray contrast material. 20. The method according to any one of claims 18 or 19, characterized in that a plurality of coatings, of which at least one contains an X-ray contrast material, are applied one above the other on the wall ( 102 ) of the tube ( 100 ). 21. The method according to claim 20, characterized in that at least one of the coatings on one underlying coating is applied before the underlying coating has been fixed. 22. The method according to any one of claims 20 or 21, characterized characterized as being the most outermost Coating essentially no X-ray contrast Contains material.