WO1989011836A1 - Prothese implantable et procede de fabrication - Google Patents

Prothese implantable et procede de fabrication Download PDF

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Publication number
WO1989011836A1
WO1989011836A1 PCT/US1989/002380 US8902380W WO8911836A1 WO 1989011836 A1 WO1989011836 A1 WO 1989011836A1 US 8902380 W US8902380 W US 8902380W WO 8911836 A1 WO8911836 A1 WO 8911836A1
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WO
WIPO (PCT)
Prior art keywords
artifact
coating
substrate
hydrogen
methane
Prior art date
Application number
PCT/US1989/002380
Other languages
English (en)
Inventor
Hirotsugu Koge Yasuda
Original Assignee
Biogold Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Biogold Inc. filed Critical Biogold Inc.
Publication of WO1989011836A1 publication Critical patent/WO1989011836A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L33/00—Antithrombogenic treatment of surgical articles, e.g. sutures, catheters, prostheses, or of articles for the manipulation or conditioning of blood; Materials for such treatment
    • A61L33/0076—Chemical modification of the substrate
    • A61L33/0088—Chemical modification of the substrate by grafting of a monomer onto the substrate
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/082—Inorganic materials
    • A61L31/088—Other specific inorganic materials not covered by A61L31/084 or A61L31/086

Definitions

  • the present invention relates to artifacts for permanent or temporary insertion or implantation into a living animal (including human) body, such artifacts or part thereof having a thin surface coating which is biocompatible at the site where the artifact is implanted.
  • the invention also relates to a method of making such an implantable artifact.
  • Artifacts or devices which are intended for use in a living animal body usually are made of materials having limited biocompatibility, such as non-thrombogenicity and compatibility vis-a-vis living tissue. Such artifacts are therefore generally coated with surface coatings for improving the biocompatibility, such coating being made without affecting other important properties of the artifact.
  • coating of implantable artifacts has been provided by so called plasma polymerization. Such technique has been used mainly when coating artifacts made of polymeric materials.
  • Plasma polymerization generally is based on introducing a gas comprising one or more polymerizable organic monomers into a vacuum zone, wherein the material to be coated is placed.
  • the polymerizable monomers are then subjected to an electric discharge for initiating polymerization reactions by the generation of ions of free radicals reacting with each other and also with the substrate when made of an organic material to form a deposit on the substrate.
  • the polymerizable monomers are often constituted by fluorinated hydrocarbons, such as tetrafluoro ethylene.
  • US patents 4,656,083 and 4,718,907 each relating to techniques for improving the biocompatibility of implantable devices or prostheses. Both patents relate to the use of fluorine-containing compounds as plasma polymerizable monomers, but both techniques suffer from shortcomings in regard to rendering the substrate sufficiently in non-thrombogenic or tissue-compatible.
  • US patent 4,718,907 aims at providing improvement of the surface of the substrate by controlling the fluorine to carbon atomic ratio so that the coating on the interior surface of the tube has a higher ratio than the exterior surface.
  • this technique aims at providing for a fluorine to carbon ratio greater than 1,5.
  • the basic concept of this prior art is to mimic or approach the properties of polytetrafluoroethylen (PTFE).
  • the object of the present invention is to provide new techniques for treating substrate materials for the purpose of improving their biocompatibility by subjecting the substrate material to plasma gas discharge in the presence of a monomeric gas capable of plasma polymerization under deposition of a biocompatible surface coating on the substrate.
  • Another object of the invention is to deposit by plasma polymerization onto the substrate a carbonaceous coating which is amorphous and mainly consists of a three-dimensional network of carbon atoms covalently bound to each other, other atoms being covalently bound to said carbon atoms which other atoms are selected from hydrogen and fluorine. Yet another object is to provide such carbonaceous coating, wherein the atomic ratio of hydrogen plus fluorine to carbon is less than about 1.3.
  • implantable artifacts can be provided with a very thin and uniform surface coating by the use of plasma polymerization.
  • the coating obtained in accordance with the present invention is of a non- -crystalline i.e. amorphous nature, and is constituted by a three-dimensional carbon to carbon covalently bound network, in which the majority of the bonds are of the sp 3 type.
  • the invention is largely based on the surprising discovery that biocompatibility through a plasma-deposited coating is substantially improved if the coating is comprised of a carbonaceous material which is amorphous and which has a structure which contrary to US patent 4,718,907 approaches that of diamond.
  • diamond is a crystalline three-dimensional network of carbons solely joined by sp 3 carbon-carbon bonds.
  • graphite is a two-dimensional planar network of carbons built up from both sp 3 and sp 2 bonds.
  • the refractive index of diamond is about 2.3 and in the coating conceived by the present invention it is preferred that the refractive index is greater than about 1.6.
  • carbon-to-carbon bonds these are thus predominantly of the sp 3 type, and it is particularly preferred that not more than about 25X of said carbon-to-carbon bonds are of the sp 2 type.
  • the techniques of the present invention make it possib le to deposit an extremely thin coating of a thickness generally less than about 1000 nm, preferably not more than about 100 nm.
  • the coating is sufficiently flexible and can accordingly be deposited on any type of substrate useful for the present purpose, such as substrates made of organic or inorganic polymeric materials or non-polymeric inorganic materials, such as metallic, ceramic, glass or composite materials.
  • substrates made of organic or inorganic polymeric materials or non-polymeric inorganic materials, such as metallic, ceramic, glass or composite materials.
  • the excellent adherence to the substrate and the flexibility of the coating makes it particularly suited for use in covering expandible stents, such as self-expanding stents of the type disclosed in US patent No. 4,655,771.
  • the invention is also of particular interest in relation to further developments of such prostheses as disclosed in published UK patent application 2 189 150.
  • the present invention also provides for a method of making implantable artifacts comprising a substrate and a thin surface coating which is biocompatible in its environment.
  • the method of the invention involves subjecting the exposed surface of the substrate to a plasma gas discharge in the presence of a monomeric gas containing monomers selected from hydrocarbons and halogenated hydrocarbons, optionally together with hydrogen, whereby there is deposited onto the substrate a thin amorphous carbonaceous layer having the desired biocompatibility, such as blood and tissue compatibility.
  • a monomeric gas containing monomers selected from hydrocarbons and halogenated hydrocarbons, optionally together with hydrogen whereby there is deposited onto the substrate a thin amorphous carbonaceous layer having the desired biocompatibility, such as blood and tissue compatibility.
  • monomers selected from fluo ⁇ nated hydrocarbons and hydrocarbons having 1 to 6 carbon atoms It is particularly preferred to use fluorinated hydrocarbons and hydrocarbons having 1, 2 or 3 carbon atoms.
  • fluorinated hydrocarbons and hydrocarbons having 1, 2 or 3 carbon atoms As examples of such monomers there may be mentioned tetrafluoroethylene, hexafluoroethane, perfluoropropylene, methane, ethane and such monomers can be used in different combmations with or without hydrogen to obtain varying atomic ratios (H+F) to C at levels less than about 1.5, preferably less than about 1.5.
  • tetrafluoroethylene and methane can be used in roughly equal proportions, and such mixtures may be diluted using hydrogen.
  • solely a pure hydrocarbon may be used as a monomeric gas.
  • mixtures of methane and hydrogen are also possible to use mixtures of methane and hydrogen.
  • a halogenated hydrocarbon in combination with hydrogen the plasma discharge will result in reactions whereby a corresponding hydrogen halogenide, such as hydrofluoric acid, escapes in gaseous form.
  • the monomeric gas is free from oxygen-containing constituents. Due to the presence of unpaired electrones, i.e. free-radicals, in the deposited coating some oxygen from the environment may be found on the surface of the coating but will not constitute any problem with regard to biocompatibility of the coating.
  • biocompatible has the meaning biologically non-interfering rather than any meaning in the direction of providing any specific bioactivity.
  • the principal object of providing a surface coating in accord with this invention is to create a biologically inert surface of a non-interfering character.
  • Articles, devices or artifacts provided by the present invention have a surface coating with outstanding properties, such as hardness, chemical inertness, surface dynamic stabi lity, excellent bonding to the substrate, and the coating is furthermore a very good barrier to the underlying substrate. These properties provide for excellent biocompatibility, corrosion resistance and general protection of the substrate. Another advantage is the fact that the coating has good resistance to sterilization by irradiation at the energy level required, such as several Mrads, using ⁇ - or ⁇ -radiation.
  • the conditions for the plasma polymerization to deposit the coating on a substrate are not of a critical nature but it is preferred to use high plasma energy density expressed as Joules per kilogram monomers and hydrogen, such value preferably being above 1 GJ/kg.
  • the minimum value varies with the type of monomeric gas used, and as examples there may be mentioned that when using methane as a monomer the value is about 8 GJ/kg, whereas when using fluorinated hydrocarbons together with hydrogen the lower value of about 1 can be used.
  • the reactor used for the plasma polymerization is quite generally of a conventional character but shall be designed to allow for sufficient residence time of reactor species in the plasma state, i.e. provision of sufficient kinetic path length before deposition occurs, and this can be achieved by combinations of plasma volume, system pressure and plasma energy density.
  • the present disclosure will enable the skilled artisan to provide implantable artifacts, such as heart valves, vascular prostheses, stents, catheters and various other devices intended for implantation for a longer period of time.
  • biocompatible coating of such artifacts having a low (H+F) to C ratio will provide for excellent thromboresistance and tissue compatibility.
  • present techniques are useful also for coating filaments (mono- or polyfilaments or yarns) which are then braided, weaved or knitted to form the final product
  • the stents and grafts modified by plasma polymerization are exposed to flowing blood using a baboon arteriovenous shunt system described by Hanson et al., Arteriosclerosis 5:595, 1985.
  • the medicinal implants were placed inside a 10 cm length of rigid-walled Teflon tubing (Small Parts Inc. Miami, Florida, USA).
  • Teflon tubings containing stents or grafts are placed between the arterial and venous silicone rubber tubing segments comprising a chronic femoral arteriovenous (A-V) shunt in baboons as described by Hanson et al. loc.cit.
  • the thrombogenicity inregard to platelet adhesion of both untreated and plasma polymer modified artifacts or deplants is determined by dynamic scintillation camera imaging of the accumulation of autologous blood platelets labeled with Ind ⁇ um-111-oxine following exposure to flowing blood in the baboon A-V shunt system. The results are expressed as the total number of platelets deposited over one hour according to the method described by Hanson et al., loc.cit.
  • the stent is fastened in the opening of the sample holding disc by means of small clips located at both ends of the opening.
  • the sample holding disc is placed at equidistance from two electrodes used in a Plasma Polymerization Apparatus of the type LCVD--12-400A, Shimadzu Corporation, Kyoto, Japan.
  • the two electrodes are assisted by magnetic enhancement providing the maximum parallel component with respect to the electric field of a magnetic field of approximately 600 Gauss and the distance between the two electrodes is approximately 120 mm.
  • the sample holding disc is rotated in such a manner that the stent will pass the center portion of plasma volume created by the two parallel electrodes at a rate of approximately 30 rpm.
  • plasma polymerization is initiated by applying 150 watts. Plasma polymerization is sustained till a stationary thickness monitor, located near the edge of the rotating substrate holding disc indicates that the accumulated thickness of deposition onto the sensor reaches approximately 100 nm, corresponding to approximately 30 nm on the rotating stent.
  • the coating prepared by the process has a refractive index of about 1.9 and an estimated value (F+H)/C of about 0.8.
  • Fig. 1 of the drawing The results of the platelet deposition experiments are illustrated in Fig. 1 of the drawing, wherein deposited platelets are plotted against blood exposure time in minutes.
  • a vascular graft of the type Goretex (W.L.Gore & Associates Inc., 111., USA) of 4 mm i.d. and length 100 mm is snugly positioned within a glass tube which is connected to a vacuum pump and a gas inlet tube at the other end.
  • Two elec trodes constituted by copper plates, width 5 mm, length 50 mm and thicknes 1 mm, are bent to surround a glass tube and are kept approximately 30 mm apart. These two electrodes are connected to 13.5MHz radio frequence power source in a floating mode.
  • stent-containmg glass tube After the stent-containmg glass tube is evacuated to less than 1 mtorr a mixture of methane and hydrogen in a ratio of one to one is introduced into the reactor system at a flow rate of 1 seem, and rf power of 50 watts is applied to the electrodes. Plasma generated by the electrodes located at the upstream side of the graft penetrates into the inside of the graft tube, and a coating of amorphous carbonaceous film having a refractive index of 1.9 and a ratio (F+H)/C of about 1.0 is applied onto the inner surface of the substrate by sustaining the plasma for one minute.
  • Four vascular grafts treated as described above are evaluated in four baboons by 60 minutes blood exposure.
  • the four treated grafts show a marked reduction in platelet accumulation as compared to seven untreated control grafts.
  • the treated grafts have accumulated only 1.4 + 0.5 x 10 9 platelets (+ 1 SEM) as compared to the untreated grafts accumulating 10.6 + 1.6 x 10 9 platelets per graft.
  • the results are illustrated in appended Fig. 2 wherein total deposited platelets are plotted against exposure time in minutes.
  • Example 3 Example 1 is repeated but using stainless steel stents having a diameter of 6 mm and a length of 150 mm. After evacuation of the reactor to approximately 1 mtorr a mixture of methane and hydrogen in the ratio of one to one is introduced into the reactor at a rate of 0.5 seem, and plasma polymerization is initiated by applying 150 watts. Plasma polymerization is sustained till a stationary thickness monitor indica tes an accumulated thickness of deposition of approximately 100 nm, corresponding to about 30 nm deposition on the rotating stent. The material prepared by this process has the refractive index 1.9, and estimated value (F+H)/C of approximately 0.8.
  • Example 3 The same apparatus as used in Example 1 is used and stainless steel stents of the same type as in Example 3 are placed on the aluminum disc of the apparatus. However, the electrodes of the reactor are replaced by a hollow anode system designed as follows.
  • the hollow anode system consists of an aluminum cup, 100 mm x 100 mm and of 50 mm depth, the cup being connected to two aluminum plates, 100 mm x 50 mm, via dielectric materials (Macor, Corning Glass, Corning, NY, USA) in the plane of the opening side of the cup.
  • One terminal of a radio frequence (rf) power supply is connected to the cup and another terminal is connected to the two plates.
  • Monomeric gas is fed into the cup through an inlet, which is attached to the back side of the cup.
  • the hollow anode system is placed parallel to the rotating disc maintaining a distance of approximately 30 mm.
  • a mixture of methane and tetrafluoroethylen in a ratio of one to one is introduced at a flow rate of 0.5 seem, and plasma polymerization is initiated by applying 50 watts.
  • the stent is coated uniformly after five minutes' operation. During this period the stent passes through plasma created in the space determined by the cup and the rotating plates, repeated passages being obtained at the rotating rate of approximately 30 rpm.
  • a piece of silicons wafer is placed on the surface of the rotating disc to collect film sample for measurement of the refractive index by Elipsometry.
  • the thin coating obtained has a refractive index of about 1.8 and a ratio (F+H)/C of about 0.7.
  • the biological properties of the coated stents are similar to those obtained with the stents treated according to Example 3.
  • a stainless steel wire used for preparing the stainless steel stent treated according to Example 1 is coated in a continuous manner by using the plasma polymerization reactor described in Example 1.
  • a feeding spool, on which approximately 100 meter of stainless steel wire is wound, and a take-up spool are placed in a vacuum vessel attached to the reactor through a vacuum joint located on the stainless steel skirt portion of the reactor.
  • the wire is fed through the center portion of the inter electrode space five times and is rewound on the take-up spool at a linear speed of approximately one meter per minute.
  • Identical conditions as to plasma polymerization as described in Example 1 are used for coating the wire.
  • a uniform coating of homogeneous, amorphous carbonaceous film (F+H)/C approximately 0.8 is applied on the surface of the wire, and then the coated wire is used to braid the stent in accordance with the disclosure of UK patent application 2 189 150.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Epidemiology (AREA)
  • Surgery (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Hematology (AREA)
  • Vascular Medicine (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Materials For Medical Uses (AREA)
  • Prostheses (AREA)

Abstract

La présente invention décrit une prothèse destinée à être implantée dans un corps animal vivant, la prothèse ou une partie de la prothèse comportant une mince couche d'enrobage de surface biocompatible avec le site où elle est implantée. La prothèse se caractérise en ce que la couche d'enrobage se compose d'un matériau carboné amorphe et essentiellement constitué par un réseau tridimensionnel d'atomes de carbone, liés par covalence entre eux et d'autres atomes liés par covalence auxdits atomes de carbone et choisis parmi des atomes d'hydrogène et de fluor, le rapport atomique entre (H+F) et C étant inférieur à 1,5. La présente invention décrit également un procédé de fabrication d'une telle prothèse.
PCT/US1989/002380 1988-06-07 1989-06-06 Prothese implantable et procede de fabrication WO1989011836A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US20309788A 1988-06-07 1988-06-07
US203,097 1988-06-07

Publications (1)

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WO1989011836A1 true WO1989011836A1 (fr) 1989-12-14

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PCT/US1989/002380 WO1989011836A1 (fr) 1988-06-07 1989-06-06 Prothese implantable et procede de fabrication

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JP (1) JPH04501965A (fr)
WO (1) WO1989011836A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2663534A1 (fr) * 1990-06-22 1991-12-27 Cuilleron J Valve cardiaque artificielle.
US20120177936A1 (en) * 2009-08-17 2012-07-12 Kawasumi Laboratories, Inc. Medical instrument and metal product
EP2072068A3 (fr) * 2007-12-20 2012-12-12 Biotronik VI Patent AG Implant composé d'un alliage biocorrodable
US8801778B2 (en) 2007-12-20 2014-08-12 Biotronik Vi Patent Ag Implant with a base body of a biocorrodible alloy
US8852693B2 (en) 2011-05-19 2014-10-07 Liquipel Ip Llc Coated electronic devices and associated methods
RU2632297C2 (ru) * 2015-12-23 2017-10-03 Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский авиационный институт (национальный исследовательский университет)" (МАИ) Нанокомпозитный материал с биологической активностью

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2803017B2 (ja) * 1993-06-07 1998-09-24 工業技術院長 抗血栓性医用材料及び医療用具並びにこれらの製造方法、製造装置及びプラズマ処理装置
JP5138127B2 (ja) * 1999-07-19 2013-02-06 テルモ株式会社 体内埋め込み医療器

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4264750A (en) * 1979-08-01 1981-04-28 Massachusetts Institute Of Technology Process for fluorinating polymers
US4656083A (en) * 1983-08-01 1987-04-07 Washington Research Foundation Plasma gas discharge treatment for improving the biocompatibility of biomaterials
US4718907A (en) * 1985-06-20 1988-01-12 Atrium Medical Corporation Vascular prosthesis having fluorinated coating with varying F/C ratio
US4743327A (en) * 1984-06-15 1988-05-10 Cordis Corporation Adhesive bonding of fluoropolymers
US4776337A (en) * 1985-11-07 1988-10-11 Expandable Grafts Partnership Expandable intraluminal graft, and method and apparatus for implanting an expandable intraluminal graft

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4264750A (en) * 1979-08-01 1981-04-28 Massachusetts Institute Of Technology Process for fluorinating polymers
US4656083A (en) * 1983-08-01 1987-04-07 Washington Research Foundation Plasma gas discharge treatment for improving the biocompatibility of biomaterials
US4743327A (en) * 1984-06-15 1988-05-10 Cordis Corporation Adhesive bonding of fluoropolymers
US4718907A (en) * 1985-06-20 1988-01-12 Atrium Medical Corporation Vascular prosthesis having fluorinated coating with varying F/C ratio
US4776337A (en) * 1985-11-07 1988-10-11 Expandable Grafts Partnership Expandable intraluminal graft, and method and apparatus for implanting an expandable intraluminal graft
US4776337B1 (en) * 1985-11-07 2000-12-05 Cordis Corp Expandable intraluminal graft and method and apparatus for implanting an expandable intraluminal graft

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2663534A1 (fr) * 1990-06-22 1991-12-27 Cuilleron J Valve cardiaque artificielle.
EP2072068A3 (fr) * 2007-12-20 2012-12-12 Biotronik VI Patent AG Implant composé d'un alliage biocorrodable
US8801778B2 (en) 2007-12-20 2014-08-12 Biotronik Vi Patent Ag Implant with a base body of a biocorrodible alloy
US20120177936A1 (en) * 2009-08-17 2012-07-12 Kawasumi Laboratories, Inc. Medical instrument and metal product
US8900291B2 (en) * 2009-08-17 2014-12-02 Kawasumi Laboratories, Inc. Medical instrument and metal product
US8852693B2 (en) 2011-05-19 2014-10-07 Liquipel Ip Llc Coated electronic devices and associated methods
RU2632297C2 (ru) * 2015-12-23 2017-10-03 Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский авиационный институт (национальный исследовательский университет)" (МАИ) Нанокомпозитный материал с биологической активностью

Also Published As

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