Material Composition Having Reduced Friction
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(19) TZZ ¥ _T (11) EP 2 863 962 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: A61L 29/04 (2006.01) A61L 29/08 (2006.01) 31.08.2016 Bulletin 2016/35 A61L 29/14 (2006.01) (21) Application number: 13725597.2 (86) International application number: PCT/EP2013/060183 (22) Date of filing: 16.05.2013 (87) International publication number: WO 2013/189672 (27.12.2013 Gazette 2013/52) (54) MATERIAL COMPOSITION HAVING REDUCED FRICTION COEFFICIENT USED FOR MEDICAL TUBES MATERIALZUSAMMENSETZUNG ZUR VERRINGERUNG DES REIBUNGSKOEFFIZIENTEN FÜR MEDIZINISCHE SCHLÄUCHE COMPOSITION DE MATIÈRE AYANT UN COEFFICIENT DE FROTTEMENT RÉDUIT UTILISÉE POUR DES TUBES MÉDICAUX (84) Designated Contracting States: • J.KOLARIK ET AL.: "High-density AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Polyethylene/cycloolefin copolymer blends. GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Part.1: Phase structure, dynamic mechanical, PL PT RO RS SE SI SK SM TR tensile, and impact properties", POLYMERIC ENGINEERING AND SCIENCE, 2005, pages (30) Priority: 20.06.2012 US 201261661812 P 817-826, XP002712371, • JAN KOLARIK ET AL.: "High-density (43) Date of publication of application: polyethylene/cycloolefin copolymer blends, 29.04.2015 Bulletin 2015/18 Part.2: non linear tensile creep", POLYMER ENGINEERING AND SCIENCE, 2006, pages (73) Proprietor: Biotronik AG 1363-1373, XP002712372, 8180 Bülach (CH) • DATABASECA [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; CONSTANT, (72) Inventor: SCHWITZER, Alwin DAVID R.: "Cyclic-olefinic copolymers as 8180 Buelach (CH) non-migrating, polymeric slip additives in", XP002712375, retrieved from STN Database (74) Representative: Randoll, Sören et al accession no. 2003:100673 & CONSTANT, DAVID Biotronik SE & Co. KG R.: "Cyclic-olefinic copolymers as Corporate Intellectual Property non-migrating, polymeric slip additives in", Woermannkehre 1 PLACE CONFERENCE, BOSTON, MA, UNITED 12359 Berlin (DE) STATES, SEPT. 9-12, 2002 , 1031-1058 PUBLISHER: TAPPI PRESS, ATLANTA, GA. (56) References cited: CODEN: 69DMQ2; ISBN: 1-930657-97-8, 2002, EP-A1- 2 186 634 EP-A2- 0 873 759 • DATABASECA [Online] CHEMICAL ABSTRACTS US-A1- 2006 093 831 SERVICE, COLUMBUS, OHIO, US; YOSHINAGA, MASANOBU: "Multilayer cycloolefin packaging • SYLVIEPIMBERT: "Evaluation of the fractionated materials with low bleeding and packaging bags crystallization of isotatic polypropylene and high manufactured from them", XP002712376, density polyethylenes in their blends with retrieved from STN Database accession no. cycloolefin copolymers", MACROMOL. SYMP., 2001:441169 & JP 2001 162724 A (TOPPAN vol. 203, 2003, pages 277-283, XP002712370, PRINTING CO., LTD., JAPAN) 6 September 2013 (2013-09-06) Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 863 962 B1 Printed by Jouve, 75001 PARIS (FR) 1 EP 2 863 962 B1 2 Description associated with the risk that these coatings, and specif- ically hydrophilic coatings, which interact with biological TECHNICAL FIELD liquids (blood), may release substances such as those which are defined in ISO 10093-17 (2002) § 3.10 and [0001] The invention relates to a mixture comprising 5 which require complex determination and classification. or consisting of polyethylene (PE) and cyclic olefin co- [0009] Against this background, it was the object of the polymer (COC), wherein a content of ≥ 70% by weight present invention to provide a novel material which is relative to the total mass of PE in the mixture is high- able to provide a surface having improved frictional be- density polyethylene (HDPE). The invention further re- havior, in particular with respect to metal, especially for lates to solid bodies, consisting of or comprising such a 10 medical applications. Moreover, it was desirable for the mixture, and to solid bodies which are medical products, corresponding material to have a property window which comprising a mixture of PE and COC. allows use of the same in a variety of medical applica- tions. In addition to biological compatibility, the properties BACKGROUND that shall be mentioned here also include properties such 15 as flexibility, trackability, conduct under tensile and/or [0002] There is a constant need for improved materials compressive stress, and/or usability in a variety of pro- for medical applications, and particularly in the field of duction methods and/or cost effectiveness in production. medical tubes and catheter guide devices. An important [0010] This object is achieved by a solid body compris- aspect are the intrinsic frictional properties, for example ing or consisting of PE and COC, wherein≥ 70% by with respect to metal, for applications in which a wire is 20 weight, preferably ≥ 90% by weight, and still more pref- to be advanced in a corresponding tube system or, in erably 100% by weight, relative to the total mass of PE, general terms, for areas in which contact may occur be- of the PE in the mixture is HDPE, and the COC content tween a surface and metal as part of the medical appli- in the PE/COC mixture preferably ranges between 5 and cations. 25% by weight, relative to the total mass of PE and COC [0003] In the prior art, high-density polyethylene25 and wherein the solid body is a medical tube. (HDPE) or polytetrafluoroethylene (PTFE) is used, for [0011] For this purpose, COC denotes cyclic olefin co- example in tubes for medical applications, so as improve polymer, PE denotes polyethylene, and HDPE denotes the frictional properties. These materials are used in par- high-density polyethylene. ticular as the inner layer of multi-layer materials. Guide [0012] Within the meaning of the present application, catheters having a PTFE inner layer, or tubes made of 30 HDPE is a special fraction of PE, wherein HDPE within HDPE, are thus known, for example, from the prior art the meaning of the present application is a PE that has as protectors for catheters. a density of ≥ 0.934 g/cm3, which is higher than that of [0004] Asan alternative, thesurfaces of tubes arecoat- LDPE (0.915- 0.933). Moreover, the crystallinityof HDPE ed in order to reduce the intrinsic material properties, so is usually higher than that of LDPE, which manifests itself, as to deliberately control the properties hydrophilically or 35 for example, in the higher melting temperature (HDPE: hydrophobically. ∼130°C, LDPE: ∼ 110°C). The higher density of HDPE [0005] A combination comprising a cyclic olefin copol- as compared to LDPE is achieved by a considerably low- ymer (COC) and a catheter is known from WOer "degree of long-chain branching". 2005/044314 A2, for example. [0013] PE, notably in the form of HDPE, is generally [0006] KR 100429660 B1 discloses combinations40 present in semi-crystalline form, which is preferred for comprising polyethylene, and more specifically mixtures the invention. In contrast, COC is present in amorphous made of low-density polyethylene (LDPE) and high-den- form. sity polyethylene (HDPE), and cyclic olefin copolymer as [0014] To the extent that the mixture according to the film material, having properties, for example chemical invention is a mixture of granules of the two polymer resistance, scratch resistance and flexibility, equal to45 types, this mixture shall be considered to be a preliminary PVC films, as replacement material for softened PVC product of the proper mixture used according to the in- (softened PVC films). vention. Using a suitable melting and mixing method, a [0007] The drawback of the existing known solutions copolymer canbe producedfrom this mixture of granules, is that the intrinsic frictional properties of polymers that the copolymer having a considerably lower friction force are presently used for medical tubing is just barely suffi- 50 than semi-crystalline HDPE, especially with respect to a cient, for example for the guide wire friction of inside metallic friction partner. Comparison experiments shafts in RX catheters. So as to prevent excessive force showed a reduction in the friction forces of approximately application when inserting the catheter on the guide wire 30%. It was not predictable from the prior art that this and possible injury to the vascular walls, cardiologists effect was achievable by a corresponding copolymer and desire catheters that have the lowest possible frictional 55 it is thus surprising. forces. [0015] Particularly good effects within the meaning of [0008] The added coating of catheter surfaces, for ex- the aforementioned desired properties of the invention, ample, with hydrophobic or hydrophilic coating agents is and especially with respect to the decrease in friction 2 3 EP 2 863 962 B1 4 forces with respect to (metallic) friction partners, can be the group of high-density polyethylene (HDPE), for ex- achieved when the weight percentage relationships be- ample Petrothene® LM 6007-00, Purel® GD 6250 or tween the total mass of PE and the total mass of COC Bormed® HE2581-PH, and the preferred amorphous in the mixture according to the invention are 60 - 98% by COC is selected from high-Tg COC types (for example weight to 40 - 2% by weight, and preferably 75 - 90% by 5 the TOPAS® products). weight to 25 - 5% by weight, based on the total mass of [0020] The desired properties windows can be PE and COC in the mixture. The aforementioned weight achieved particularly well when using the aforemen- percentage relationship still more preferably is 80 - 95% tioned preferred and particularly preferred materials. by weight to 20 - 5% by weight. [0021] The invention relates to a solid body, preferably [0016] A possible explanation for the resulting advan- 10 to an extrusion product, for example a profiled, tube.