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EP2443191A1 - Radio-opaque shape memory polymers - Google Patents

Radio-opaque shape memory polymers

Info

Publication number
EP2443191A1
EP2443191A1 EP10720354A EP10720354A EP2443191A1 EP 2443191 A1 EP2443191 A1 EP 2443191A1 EP 10720354 A EP10720354 A EP 10720354A EP 10720354 A EP10720354 A EP 10720354A EP 2443191 A1 EP2443191 A1 EP 2443191A1
Authority
EP
European Patent Office
Prior art keywords
shape memory
memory polymers
polymers according
biocl
polymer
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP10720354A
Other languages
German (de)
French (fr)
Inventor
Matthias Lergenmueller
Sabine Schoen
Adolf Pfaff
Karl-Friedrich Reichenbach
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Adolf Pfaff & Karl-Friedrich Reichenbach GbR
Merck Patent GmbH
Adolf Pfaff Dr Karl Friedrich Reichenbach GbR vertretungsberechtigter Gesellschafter
Original Assignee
Adolf Pfaff & Karl-Friedrich Reichenbach GbR
Merck Patent GmbH
Adolf Pfaff Dr Karl Friedrich Reichenbach GbR vertretungsberechtigter Gesellschafter
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 Adolf Pfaff & Karl-Friedrich Reichenbach GbR, Merck Patent GmbH, Adolf Pfaff Dr Karl Friedrich Reichenbach GbR vertretungsberechtigter Gesellschafter filed Critical Adolf Pfaff & Karl-Friedrich Reichenbach GbR
Publication of EP2443191A1 publication Critical patent/EP2443191A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • A61L27/14—Macromolecular materials
    • 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
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • 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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/04—Macromolecular materials
    • 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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
    • 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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
    • A61L29/18—Materials at least partially X-ray or laser opaque
    • 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
    • A61L31/04—Macromolecular materials
    • 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
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • 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
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/18—Materials at least partially X-ray or laser opaque
    • 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
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/16—Materials with shape-memory or superelastic properties

Definitions

  • the present invention relates to shape memory polymers, which are characterized in that they as
  • X-ray contrast agent containing BiOCl pigments Such doped polymers find particular application in medical devices, e.g. Stiffening pins for the spine, tooth root canal pins, as bone cement and in catheter materials.
  • Radioopaque additives e.g. Barium sulfate, zirconium dioxide, zinc oxide and iodine-containing compounds are used in a number of medical technology applications to make the medical device product visible on an X-ray after use - or to be able to track it dynamically. Common applications are u.a.
  • Radiopacity is one of the many requirements for tooth root canal filling materials.
  • the radiopacity of a root canal sealer is intended to assess the homogeneity of the root canal filling and the detection of blisters and cracks in the root canal
  • New X-ray devices work with increasingly higher energies (kVp) in the X-ray irradiation, which to produce the same visibility either higher use concentrations of known filling materials such.
  • kVp energies
  • Barium sulfate or require fillers having a higher radioopacity. Since with increasing use concentration, for example, barium sulfate, the properties of the material are severely and partially adversely affected, for example, with respect to the elasticity of the material, materials are sought, which in this regard have a more neutral behavior and not or only materially affect the material properties.
  • Shape memory polymers in particular shape memory plastics (SMPs), are materials that can change their external shape under the influence of an external stimulus.
  • SMPs shape memory plastics
  • Thermosensitive shape memory plastics are of particular importance in medical technology.
  • the shape memory effect is not a specific material property of individual polymers; Rather, it results directly from the 5 combination of polymer structure and polymer morphology.
  • Shape memory plastics are able to resume their original shape after being temporarily deformed.
  • This memory can be stimulated by an external stimulus, for example by an increase in the ambient temperature or by the incorporation of finely divided magnetic nanoparticles of iron oxide into the plastic, which convert the energy of a magnetic field into heat.
  • the shape memory polymer eg a dental root pin made therefrom, reaches the so-called switching temperature at 37 ° C. within a short time after use in the human body.
  • the resilience of the polymer then causes the tooth root canal pin to be enlarged to a precisely definable extent, so that the tooth root canal is completely filled 0 and optimal fit is achieved and the entire
  • Root canal system permanently hermetically sealed and biocompatible.
  • the 5 continuous X-ray contrast medium barium sulfate is such an adverse effect that the shape memory effect in the individual switching temperature of the polymer is not fully effective and the brittleness of the plastic increases. As a result, cracks and / or fractures increasingly occur during cold-forming of the plastic.
  • the currently used contrast agents such as
  • the object of the present invention is to provide an additive with higher photon absorption, which has good biocompatibility, is non-toxic and can be incorporated very well into a shape-memory polymer and has little or no effect on the shape of the shape. Memory effect has.
  • BiOCl pigments are very suitable as radiopaque additives in shape memory polymers
  • Polymers containing platelet-shaped BiOCl pigments are distinguished by the fact that the use of BiOCl pigments in shape-memory polymers leads to elastic materials which are
  • the present invention thus relates to shape memory polymers containing as a radiopaque additive BiOCl pigments.
  • the present invention furthermore relates to the use of the shape memory polymers according to the invention as a material in medical technology, for example as bone cement or for production - A -
  • shaped articles e.g. Tooth root canal pins, stiffening pins, e.g. for the spine, vascular implants, z.
  • stiffening pins e.g. for the spine
  • vascular implants e.g. for the spine
  • stents catheters and at
  • Shape memory polymers are described in the prior art, for example in DE 198 12 160 C1, US Pat. No. 5,962,004, US Pat. No. 5,716,410, WO 99/42528, US Pat. No. 5,458,935, DE 197 55 872 and A. Lendlein, S. Kelch. memory polymers ", Angew. Chem. Int. Ed. 2002, 41 . , 2034-2057.
  • Suitable shape memory polymers are preferably composed of thermoplastic polyurethanes (TPU), furthermore polyvinyl chloride (PVC), polystyrene (PS), polyesters, polyvinyl alcohol, polyvinylsiloxane or polycarbonate, and mixtures, as well as graft and copolymers of said materials.
  • TPU thermoplastic polyurethanes
  • PVC polyvinyl chloride
  • PS polystyrene
  • polyesters polyvinyl alcohol
  • polyvinylsiloxane or polycarbonate polycarbonate
  • shape memory polymers having a Shore hardness of 5OA to 8OD, most preferably having a Shore hardness of 55A to 75D.
  • the Shore hardness is a material characteristic value for elastomers and plastics and is specified in the DIN 53505 and DIN 7868 standards.
  • shape memory polymers preferably made of TPU, with a Shore hardness of 55D to 7OD are suitable.
  • the shape memory polymers have a recovery temperature of 35 to 50 ° C.
  • thermoplastic polyurethanes are suitable, in particular aliphatic, polycarbonate-based thermoplastic polyurethanes, as they for example from Lubrizol Advanced Materials as Thermedics TM
  • TPU Tecoflex ® aliphatic, polyether-based TPU
  • Tecophilic ® TPU (aliphatic, polyether-based TPU), Tecoplast ® TPU, (aromatic, polyether-based TPU), Tecothane ® TPU (aromatic, polyether-based TPU) Estane ® TPU (aromatic polyester-based and polyether TPU) ⁇ in a wide range of hardnesses and colors are commercially available. All of these polymers are suitable for use as medically pure biomaterials.
  • the carbothanes have an extremely high hydrolytic stability and oxidation stability, which indicates excellent long-term biostability and is therefore used in particular as 5 reinforcing pins in spinal columns, as stents and for dental root canal posts.
  • thermoplastics in questions, such as. thermoplastic polyurethanes, polyvinyl chloride (PVC), polystyrene (PS), polyesters, polyvinyl alcohols, polyvinylsiloxanes and
  • the root canal pins of the shape memory polymers preferably contain 5-50% by weight of BiOCl pigments, in particular 10-30
  • Shape memory polymers for the production of catheters are preferably made of PU, PVC, polyester, polypropylene or polyethylene and mixtures, as well as graft and copolymers of said materials, as well as polytetrafluoroethylene (PTFE) containing materials.
  • the catheters made of the shape-memory polymers preferably contain 5 to 50% by weight of BiOCl pigments, in particular 10 to 30% by weight, based on the total mass of the catheter material.
  • Shape memory polymers for the use of vortex stiffeners 5 are preferably made of thermoplastic polyurethanes,
  • the vortex stiffeners of the shape memory polymers preferably contain 5 to 5 % by weight of BiOCl pigments, in particular 15 to 30% by weight, based on the total mass of the compound.
  • the BiOCl pigments can also find use in shape memory polymers for the production of bone cements.
  • the proportion of 1 ⁇ BiOCl pigment in the bone cement (polymer) is preferably 5 to 50% by weight, in particular 10 to 30% by weight, based on the total mass of the bone cement.
  • the use concentration of the BiOCl pigment in shape memory polymers 1 5 depends on the polymers used.
  • the BiOCl pigments are added to the polymer in amounts of 5 to 50% by weight, preferably 10 to 40% by weight, in particular 10 to 30% by weight, based on the total mass.
  • the BiOCl pigment in addition to the function as x-ray contrast agents can serve the BiOCl pigment as a filler and thus positively influence the deformability, elasticity, stretching bility of the plastic. If the BiOCl pigment is used only as an X-ray contrast agent, the use concentration in the range of 5 to 50 wt.%, Preferably 10 to 40 wt.%,
  • BiOCl pigments are known, e.g. from DE-PS 10 03 377, U.S. 2,975,053, DE 24 11 966, EP 0 496 686 B1 and DE 43 05 280 A1 and
  • BiOCl ⁇ ® are commercially available and are, for example, by the company. Merck KGaA, Germany, under the brand name Bi-Flair ®, Biron ®, TM and RonaFlair by the company. BASF under the brand Mearlite ®.
  • the commercially available BiOCl pigments have particle sizes of 1-50 microns. For the use of BiOCI pigments in memory-shape plastics
  • BiOCl pigments having particle sizes of 2-50 .mu.m, in particular 5-20 .mu.m, and most preferably of ⁇ 15 microns, are suitable. Due to the diverse production possibilities, the flat chenförmig BiOCI pigments with different optical properties, from matt to glossy and from transparent to opaque available.
  • the size of the individual particles for the high-gloss Bi- OCI pigments is preferably 6-20 microns, especially 8-18 microns and most preferably 10-16 microns.
  • the BiOCl pigments are uncoated, are platelets, and become loose powders in the production of the shape memory polymer
  • the shape memory polymers according to the invention are prepared, for example, by compounding the BiOCl pigment into the plastic. Furthermore, the BiOCl pigment can be added and mixed directly before or during the polymerization of the selected plastic in powder form, so that a separate compounding is avoided. The latter method is preferred since the platelet structure of the BiOCl pigment is significantly less due to this gentle incorporation
  • the preparation of the inventively doped shape memory polymer is usually carried out so that presented in a suitable mixer, the plastic granules, wetted with any additives and then the BiOCl pigment is added and mixed.
  • granules can be added during the incorporation of the BiOCl pigment optionally adhesives, organic polymer-compatible solvents, stabilizers and / or under the working conditions temperature-stable surfactants.
  • the pigmentation of the plastic usually takes place via a color concentrate (masterbatch) or compound.
  • the mixture can then be processed directly in an extruder or an injection molding machine.
  • the shaped bodies formed during processing show a very homogeneous distribution of the BiOCl pigment.
  • the invention also relates to molded parts, in particular for medical 3 ⁇ technical products comprising the inventive shape memory polymers containing BiOCl pigments.
  • inventive shape memory polymers containing BiOCl pigments are particularly suitable for the preparation of Zahnrurzelkanaluggen, reinforcing pins for the spine, catheter materials, vascular implants, such as stents, ⁇ Implantationstosmitteln.
  • the implants of the shape memory polymer of the present invention are such that they contain at least one medicinal agent, e.g. cytostatics,
  • antiangiogenic active substances corticoids, NSAID, heparin, hirudin, which is optionally delivered in high concentration and over a prolonged period to the surrounding tissue.
  • active ingredients can be added directly to the monomer in the polymerization and then homogeneous in the plastic powder or plastic granules
  • the active ingredient (s) are preferably dissolved or dispersed in the polymer, the dissolution of the active ingredient being carried out both in the melt and in the organic solution of the polymer
  • ⁇ u can.
  • an active ingredient admixture up to 30 wt.% Active ingredient in the polyurethane can be achieved.
  • the processing is carried out as described above by extrusion or injection molding, wherein only thermally stable active ingredients can be used in the extrusion or injection molding process. 25
  • the present invention also provides the use of the radiopaque shape memory polymers of the invention as an implant material, e.g. for the preparation of dental root canal pins, stiffening pins, z.
  • implant material e.g. for the preparation of dental root canal pins, stiffening pins, z.
  • spinal and rib bone, hip and knee joints for the production of bone cements, vascular grafts, stents, catheters, e.g. Bladder catheters, venous catheters, central venous catheters, heart catheters, for the production of implantation aids, for the production of reference pens for various applications in the medical field.
  • the final products are characterized by a very good radio opacity.
  • Carbothane PC 3572D (Lubrizol) is mixed with 40% as in Example 1.
  • RonaFlair TM LF-2000 (BiOCl pigment particle size 2-35 microns from Merck KGaA) compounded and granulated.
  • the granules are filled in the hopper of the injection molding machine, heated and injected under high pressure into the cavities of the tool. That way
  • the final products are characterized by a very good radio opacity.
  • Carbothane PC 3572D (Lubrizol) is compounded with 45% RonaFlair TM Fines (BiOCl pigment of particle size 2-35 ⁇ m from Merck KGaA) and granulated analogously to Example 1.
  • the granules are filled in the hopper of the injection molding machine, heated and injected under high pressure into the cavities of the tool. That way
  • the final products are characterized by a very good radio opacity.
  • Carboethane PC 3572D from Lubrizol is admixed with 25% RonaFlair TM B-50 (BiOCl pigment of particle size 2-35 ⁇ m from Merck KGaA) and converted by heating to a viscous consistency and then taken to an extruder.
  • the tough plastic compound compacted with and through an opening for shaping in the
  • the extrusion tool is a hollow tool, into which the plastic plastic compound is pressed in on one side through the extruder and leaves it on the other side as a finished tube.
  • the mass flow becomes too this purpose is split within the tool by a mandrel holder and thereby flows around the dome, which forms the cavity in the hose. While the tubing volume is determined by the mandrel, the diameter of the nozzle through which the material flow exits is responsible for the outer cross-section of the tubing.
  • the material-specific shrinkage properties of the plastic during cooling affect the dimensions of the final product.
  • the final product is characterized by its excellent radiopacity.

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  • Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Surgery (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Dermatology (AREA)
  • Transplantation (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Materials For Medical Uses (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
  • Dental Preparations (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to shape memory polymers characterized in that they comprise BiOCI pigments as X-ray contrast agents. Such doped polymers are used particularly in medical technology products, such as reinforcing pins for the spinal column, tooth root pins, as bone cement, and in catheter materials.

Description

Radioopake Formgedächtnis-Polymere Radioopaque shape memory polymers
Die vorliegende Erfindung betrifft Formgedächtnis-Polymere (Shape Memory Polymers), die sich dadurch auszeichnen, dass sie alsThe present invention relates to shape memory polymers, which are characterized in that they as
Röntgenkontrastmittel BiOCI-Pigmente enthalten. Derartig dotierte Polymere finden insbesondere ihre Anwendung in medizintechnischen Produkten, wie z.B. Versteifungsstifte für die Wirbelsäule, Zahnwurzelkanalstiften, als Knochenzement und in Kathetermaterialien. 0X-ray contrast agent containing BiOCl pigments. Such doped polymers find particular application in medical devices, e.g. Stiffening pins for the spine, tooth root canal pins, as bone cement and in catheter materials. 0
Radioopake Zusatzstoffe, wie z.B. Bariumsulfat, Zirkoniumdioxid, Zinkoxid und Jodhaltige Verbindungen, werden in einer Reihe von medizintechnischen Anwendungen eingesetzt, um nach Einsatz das medizintechnische Produkt per Röntgenaufnahme sichtbar zu machen ^ oder auch dynamisch verfolgen zu können. Gängige Einsatzmöglichkeiten sind u.aRadioopaque additives, e.g. Barium sulfate, zirconium dioxide, zinc oxide and iodine-containing compounds are used in a number of medical technology applications to make the medical device product visible on an X-ray after use - or to be able to track it dynamically. Common applications are u.a.
- Bariumsulfat in KathetermaterialienBarium sulfate in catheter materials
- Bariumsulfat oder Zirkoniumdioxid in Knochenzementen ^ - Bariumsulfat in teilelastischen Versteifungsstiften zurBarium sulphate or zirconium dioxide in bone cements Barium sulphate in partially elastic stiffening pins
Wirbelsäulenstabilisierungspinal stabilization
- Bariumsulfat und/oder Zinkoxid in Guttapercha-Stiften zur Zahnwurzelkanalbehandlung. ^ Beispielsweise ist Radioopazität eine der zahlreichen Anforderungen an Zahnwurzelkanalfüllmaterialien. Die Radioopazität eines Wurzelkanal- sealers soll dabei eine Beurteilung der Homogenität der Wurzelkanalfüllung und die Erkennung von Blasen und Rissen in derBarium sulphate and / or zinc oxide in gutta-percha pins for tooth root canal treatment. For example, radiopacity is one of the many requirements for tooth root canal filling materials. The radiopacity of a root canal sealer is intended to assess the homogeneity of the root canal filling and the detection of blisters and cracks in the root canal
Wurzelkanalfüllung erleichtern. 0Facilitate root canal filling. 0
Neue Röntgengeräte arbeiten mit zunehmend höheren Energien (kVp) bei der Röntgenbestrahlung, welche zur Erzeugung gleicher Sichtbarkeit entweder höhere Einsatzkonzentrationen der bekannten Füllmaterialien, wie z. B. Bariumsulfat, verlangen oder Füllmaterialien erfordern, die eine5 höhere Radioopazität aufweisen. Da mit zunehmender Einsatzkonzentration beispielsweise an Bariumsulfat die Eigenschaften des Werkstoffes stark und zum Teil negativ beeinträchtigt werden, z.B. bezüglich der Elastizität des Werkstoffs, werden Materialien gesucht, die diesbezüglich ein neutraleres Verhalten aufweisen und die Werkstoffeigenschaften nicht oder nur unwesentlich beeinflussen.New X-ray devices work with increasingly higher energies (kVp) in the X-ray irradiation, which to produce the same visibility either higher use concentrations of known filling materials such. Barium sulfate, or require fillers having a higher radioopacity. Since with increasing use concentration, for example, barium sulfate, the properties of the material are severely and partially adversely affected, for example, with respect to the elasticity of the material, materials are sought, which in this regard have a more neutral behavior and not or only materially affect the material properties.
Formgedächtnis-Polymere (FGP), insbesondere Formgedächtnis-^ kunststoffe (shape memory plastics = SMPs) sind Werkstoffe, die unter Einwirkung eines externen Stimulus ihre äußere Form verändern können. In der Medizintechnik sind insbesondere thermosensitive Formgedächtniskunststoffe von Bedeutung. Der Formgedächtniseffekt ist dabei keine spezifische Stoffeigenschaft einzelner Polymere; vielmehr resultiert er5 unmittelbar aus der Kombination von Polymerstruktur und Polymermorphologie.Shape memory polymers (FGP), in particular shape memory plastics (SMPs), are materials that can change their external shape under the influence of an external stimulus. Thermosensitive shape memory plastics are of particular importance in medical technology. The shape memory effect is not a specific material property of individual polymers; Rather, it results directly from the 5 combination of polymer structure and polymer morphology.
Formgedächtniskunststoffe sind in der Lage ihre ursprüngliche Gestalt nach zwischenzeitlicher Verformung wieder anzunehmen. Anregen lässt^ sich dieses Erinnerungsvermögen durch einen äußeren Reiz, beispielsweise durch eine Erhöhung der Umgebungstemperatur oder durch die Einarbeitung von fein verteilten magnetischen Nanoteilchen aus Eisenoxid in den Kunststoff, welche die Energie eines magnetischen Feldes in Wärme umwandeln. Beispielsweise erreicht das Formgedächtnis-Polymer,^ z.B. ein daraus hergestellter Zahnwurzelkanalstift, nach dem Einsatz im menschlichen Körper, innerhalb kurzer Zeit die sogenannte Schalttemperatur bei 37 0C. Das Rückstellvermögen des Polymers bewirkt dann die Vergrößerung des Zahnwurzelkanalstiftes auf ein genau definierbares Maß, so dass der Zahnwurzelkanal komplett aufgefüllt wird0 und eine optimale Passfähigkeit erzielt wird und das gesamteShape memory plastics are able to resume their original shape after being temporarily deformed. This memory can be stimulated by an external stimulus, for example by an increase in the ambient temperature or by the incorporation of finely divided magnetic nanoparticles of iron oxide into the plastic, which convert the energy of a magnetic field into heat. For example, the shape memory polymer, eg a dental root pin made therefrom, reaches the so-called switching temperature at 37 ° C. within a short time after use in the human body. The resilience of the polymer then causes the tooth root canal pin to be enlarged to a precisely definable extent, so that the tooth root canal is completely filled 0 and optimal fit is achieved and the entire
Wurzelkanalsystem dauerhaft hermetisch und biokompatibel verschlossen ist.Root canal system permanently hermetically sealed and biocompatible.
Beim Einsatz von Zahnwurzelkanalstiften auf Basis von Formgedächtnis-5 Polymeren zeigt das gängige Röntgenkontrastmittel Bariumsulfat einen negativen Einfluss dergestalt, dass der Shape-Memory-Effekt bei der individuellen Schalttemperatur des Polymers nicht mehr voll wirksam wird und die Sprödigkeit des Kunststoffes zunimmt. Dadurch treten beim Kaltverformen des Kunststoffes zunehmend Risse und/oder Brüche auf. In Knochenzementen weisen die derzeit verwendeten Kontrastmittel, wieThe use of tooth root canal posts based on shape memory polymers, the 5 continuous X-ray contrast medium barium sulfate is such an adverse effect that the shape memory effect in the individual switching temperature of the polymer is not fully effective and the brittleness of the plastic increases. As a result, cracks and / or fractures increasingly occur during cold-forming of the plastic. In bone cements, the currently used contrast agents, such as
5 z.B. Bariumsulfat, nicht mehr die gewünschte Röntgensichtbarkeit auf und beeinflussen die Elastizität des Zementes negativ. Weiterhin wird die Viskositätseinstellung von Knochenzementen mit zunehmendem Einsatz von radiopaken Füllstoffen schwieriger. Im Allgemeinen nimmt die Viskosität bei höheren Einsatzkonzentrationen über Gebühr zu, so dass5 e.g. Barium sulfate, no longer have the desired radiopacity and negatively affect the elasticity of the cement. Furthermore, the viscosity adjustment of bone cements becomes more difficult as the use of radiopaque fillers increases. In general, the viscosity increases excessively at higher use levels, so that
' ® die Verarbeitung, z.B. das Einspritzen durch Kanülen, erschwert ist.'® the processing, e.g. the injection through cannulas, is difficult.
Die Aufgabe der vorliegenden Erfindung ist es einen Zusatzstoff mit höherer Photonenabsorption bereitzustellen, der über eine gute Biokompatibilität verfügt, nicht toxisch ist und sich sehr gut in ein Shape- ' ^ Memory-Polymer einarbeiten lässt und keinen oder nur einen geringen Einfluss auf den Shape-Memory-Effekt hat.The object of the present invention is to provide an additive with higher photon absorption, which has good biocompatibility, is non-toxic and can be incorporated very well into a shape-memory polymer and has little or no effect on the shape of the shape. Memory effect has.
Überraschenderweise wurde nun gefunden, dass BiOCI-Pigmente sich sehr gut als radioopake Zusatzstoffe in Shape-Memory-Polymeren eignen,Surprisingly, it has now been found that BiOCl pigments are very suitable as radiopaque additives in shape memory polymers,
20 da sie neben ihrer Wirkung als Röntgenkontrastmittel nicht toxisch sind, keine Eigenfarbe aufweisen und sich sehr gut in die Polymere einarbeiten lassen. Polymere enthaltend plättchenförmige BiOCI-Pigmente zeichnen sich dadurch aus, dass der Einsatz von BiOCI-Pigmenten in Shape- Memory-Polymeren zu elastischen Materialien führt, welche sich20 since they are not toxic in addition to their effect as X-ray contrast agent, have no intrinsic color and can be incorporated very well in the polymers. Polymers containing platelet-shaped BiOCl pigments are distinguished by the fact that the use of BiOCl pigments in shape-memory polymers leads to elastic materials which are
25 kaltverformen lassen und weiterhin den Shape-Memory-Effekt bei gleicher bzw. annähernd gleicher Rückstelldynamik aufweisen. Dies bedeutet, dass bei einer bestimmten Schalttemperatur (üblicherweise Körpertemperatur bei zu inkorporierenden Medizintechnik-Produkten) eine vorher definierte Form nach einem Streck-/Reck-/Verformungsschritt wieder vollständig ou eingenommen wird.25 cold forming and continue to have the shape memory effect at the same or approximately the same restoring dynamics. This means that at a certain switching temperature (usually body temperature to be incorporated medical products) a predefined form after a stretching / stretching / molding step is taken again completely ou.
Gegenstand der vorliegenden Erfindung sind somit Formgedächtnis- Polymere, die als radioopaken Zusatzstoff BiOCI-Pigmente enthalten.The present invention thus relates to shape memory polymers containing as a radiopaque additive BiOCl pigments.
35 Gegenstand der vorliegenden Erfindung ist weiterhin die Verwendung der erfindungsgemäßen Formgedächtnis-Polymere als Werkstoff in der Medizintechnik, beispielsweise als Knochenzement oder zur Herstellung - A -The present invention furthermore relates to the use of the shape memory polymers according to the invention as a material in medical technology, for example as bone cement or for production - A -
von Formkörpern, wie z.B. Zahnwurzelkanalstifte, Versteifungsstifte, z.B. für die Wirbelsäule, Gefäßimplantate, z. B. Stents, Kathetern und beishaped articles, e.g. Tooth root canal pins, stiffening pins, e.g. for the spine, vascular implants, z. As stents, catheters and at
Implantationshilfsmitteln.Implantation tools.
In Wirbelverstärkungen wird die Sichtbarkeit der Verstärkung durch den Einsatz von BiOCI-Pigmenten ohne Beeinträchtigung der Elastizität signifikant erhöht. Vergleichbare Beobachtungen werden an Knochenzementen und Kathetern gemacht, deren Flusseigenschaften, bzw. Elastizität durch den Einsatz von BiOCI-Pigmenten nicht negativ beeinflusst werden.In vertebral reinforcements, the visibility of the reinforcement is significantly increased by the use of BiOCl pigments without affecting the elasticity. Similar observations are made on bone cements and catheters whose flow properties or elasticity are not adversely affected by the use of BiOCl pigments.
Formgedächtnis-Polymere sind im Stand der Technik beschrieben, beispielsweise in DE 198 12 160 C1 , US 5,962,004, US-Patent 5,716,410, WO 99/42528, U.S. 5,458,935, DE 197 55 872 und A. Lendlein, S. Kelch, "Shape-memory polymers", Angew. Chem. Int. Ed. 2002, 41., 2034-2057.Shape memory polymers are described in the prior art, for example in DE 198 12 160 C1, US Pat. No. 5,962,004, US Pat. No. 5,716,410, WO 99/42528, US Pat. No. 5,458,935, DE 197 55 872 and A. Lendlein, S. Kelch. memory polymers ", Angew. Chem. Int. Ed. 2002, 41 . , 2034-2057.
Geeignete Formgedächtnis-Polymere bestehen vorzugsweise aus thermoplastischen Polyurethanen (TPU), ferner aus Polyvinylchlorid (PVC), Polystyrol (PS), Polyester, Polyvinylalkohol, Polyvinylsiloxan oder Polycarbonat, und Mischungen, sowie Pfropf- und Copolymeren der genannten Materialien.Suitable shape memory polymers are preferably composed of thermoplastic polyurethanes (TPU), furthermore polyvinyl chloride (PVC), polystyrene (PS), polyesters, polyvinyl alcohol, polyvinylsiloxane or polycarbonate, and mixtures, as well as graft and copolymers of said materials.
Insbesondere bevorzugt sind Formgedächtnis-Polymere mit einer Shore- Härte von 5OA bis 8OD, ganz besonders bevorzugt mit einer Shore-Härte von 55A bis 75D. Die Shore-Härte ist ein Werkstoffkennwert für Elastomere und Kunststoffe und ist in den Normen DIN 53505 und DIN 7868 festgelegt. Für Zahnwurzelkanalstifte sind insbesondere Formgedächtnis-Polymere, vorzugsweise aus TPU, mit einer Shore-Härte von 55D bis 7OD geeignet.Particularly preferred are shape memory polymers having a Shore hardness of 5OA to 8OD, most preferably having a Shore hardness of 55A to 75D. The Shore hardness is a material characteristic value for elastomers and plastics and is specified in the DIN 53505 and DIN 7868 standards. For tooth root canal pins in particular shape memory polymers, preferably made of TPU, with a Shore hardness of 55D to 7OD are suitable.
Vorzugsweise zeigen die Formgedächtnis-Polymere eine Rückstelltemperatur von 35 bis 50 0C auf.Preferably, the shape memory polymers have a recovery temperature of 35 to 50 ° C.
Als Implantate und zur Herstellung von Kathetern sind insbesondere aliphatische thermoplastische Polyurethane geeignet, insbesondere aliphatische, polycarbonatbasierte thermoplastische Polyurethane, wie sie beispielsweise von der Fa. Lubrizol Advanced Materials als Thermedics™As implants and for the production of catheters, in particular aliphatic thermoplastic polyurethanes are suitable, in particular aliphatic, polycarbonate-based thermoplastic polyurethanes, as they for example from Lubrizol Advanced Materials as Thermedics ™
Polymer Products unter den MarkennamenPolymer Products under the brand names
Carbothane® TPU (aliphatische, auf Polycarbonat basierende TPU), Tecoflex® TPU (aliphatische, auf Polyether basierende TPU), ® Carbothane TPU (aliphatic, polycarbonate-based TPU), TPU Tecoflex ® (aliphatic, polyether-based TPU),
Tecophilic® TPU (aliphatische, auf Polyether basierende TPU), Tecoplast® TPU, (aromatische, auf Polyether basierende TPU), Tecothane® TPU (aromatische, auf Polyether basierende TPU) Estane® TPU (aromatische, auf Polyester und Polyether basierende TPU) υ in einer großen Bandbreite von Härtegraden und Farben im Handel erhält sind. Alle diese Polymere sind geeignet für den Einsatz als medizinisch reine Biomaterialien. Die Carbothane weisen eine außerordentlich hohe hydrolytische Stabilität und Oxidationsstabilität auf, welche auf eine ausgezeichnete Langzeitbiostabilität hinweist und daher insbesondere als5 Verstärkungsstifte in Wirbelsäulen, als Stents und für Zahnwurzelkanalstifte Einsatz findet.Tecophilic ® TPU (aliphatic, polyether-based TPU), Tecoplast ® TPU, (aromatic, polyether-based TPU), Tecothane ® TPU (aromatic, polyether-based TPU) Estane ® TPU (aromatic polyester-based and polyether TPU) υ in a wide range of hardnesses and colors are commercially available. All of these polymers are suitable for use as medically pure biomaterials. The carbothanes have an extremely high hydrolytic stability and oxidation stability, which indicates excellent long-term biostability and is therefore used in particular as 5 reinforcing pins in spinal columns, as stents and for dental root canal posts.
Für Zahnwurzelkanalstifte kommen insbesondere Thermoplasten in Fragen, wie z.B. thermoplastische Polyurethane, Polyvinylchlorid (PVC),^ Polystyrol (PS), Polyester, Polyvinylalkohole, Polyvinylsiloxane undFor tooth root canal pins in particular thermoplastics in questions, such as. thermoplastic polyurethanes, polyvinyl chloride (PVC), polystyrene (PS), polyesters, polyvinyl alcohols, polyvinylsiloxanes and
Mischungen, sowie Pfropf- und Copolymeren der genannten Materialien. Vorzugsweise enthalten die Wurzelkanalstifte aus den Shape-Memory- Polymeren 5-50 Gew.% an BiOCI-Pigmenten, insbesondere 10 - 30Mixtures, as well as graft and copolymers of the materials mentioned. The root canal pins of the shape memory polymers preferably contain 5-50% by weight of BiOCl pigments, in particular 10-30
Gew.%, bezogen auf die Gesamtmasse des Compounds. 5% By weight, based on the total mass of the compound. 5
Shape-Memory-Polymere für die Herstellung von Kathetern bestehen vorzugsweise aus PU, PVC, Polyester, Polypropylen oder Polyethylen und Mischungen, sowie Pfropf- und Copolymeren der genannten Materialien, sowie Polytetrafluorethylen (PTFE) enthaltende Materialien. Vorzugsweise^ enthalten die Katheter aus den Shape-Memory-Polymeren 5 - 50 Gew.% an BiOCI-Pigmenten, insbesondere 10 - 30 Gew.%, bezogen auf die Gesamtmasse des Kathetermaterials.Shape memory polymers for the production of catheters are preferably made of PU, PVC, polyester, polypropylene or polyethylene and mixtures, as well as graft and copolymers of said materials, as well as polytetrafluoroethylene (PTFE) containing materials. The catheters made of the shape-memory polymers preferably contain 5 to 50% by weight of BiOCl pigments, in particular 10 to 30% by weight, based on the total mass of the catheter material.
Shape-Memory-Polymere für den Einsatz von Wirbelversteifungen5 bestehen vorzugsweise aus thermoplastischen Polyurethanen,Shape memory polymers for the use of vortex stiffeners 5 are preferably made of thermoplastic polyurethanes,
Carbothane® TPU, Tecoflex® TPU, Tecophilic® TPU, Tecoplast® TPU, Tecothane® TPU, Estane® TPU, Polyvinylchlorid (PVC), Polystyrol (PS), Polyester, Polyvinylalkohole, Polyvinylsiloxane und Mischungen, sowie Pfropf- und Copolymeren der genannten Materialien. Vorzugsweise enthalten die Wirbelversteifungen aus den Shape-Memory-Polymere 5 - 5 50 Gew.% an BiOCI-Pigmenten, insbesondere 15 - 30 Gew.%, bezogen auf die Gesamtmasse des Compounds. ® Carbothane TPU, TPU ® Tecoflex, Tecophilic ® TPU, TPU Tecoplast ®, ® Tecothane TPU, TPU Estane ®, polyvinyl chloride (PVC), polystyrene (PS), Polyesters, polyvinyl alcohols, polyvinyl siloxanes and mixtures, as well as graft and copolymers of the materials mentioned. The vortex stiffeners of the shape memory polymers preferably contain 5 to 5 % by weight of BiOCl pigments, in particular 15 to 30% by weight, based on the total mass of the compound.
Weiterhin können die BiOCI-Pigmente auch Einsatz in Shape-Memory- Polymeren für die Herstellung von Knochenzementen finden. Der Anteil an 1^ BiOCI-Pigment im Knochenzement (Polymer) beträgt vorzugsweise 5 - 50 Gew.%, insbesondere 10 - 30 Gew.%, bezogen auf die Gesamtmasse des Knochenzements.Furthermore, the BiOCl pigments can also find use in shape memory polymers for the production of bone cements. The proportion of 1 ^ BiOCl pigment in the bone cement (polymer) is preferably 5 to 50% by weight, in particular 10 to 30% by weight, based on the total mass of the bone cement.
Die Einsatzkonzentration des BiOCI-Pigments in Formgedächtnis- 1 5 Polymeren ist aber abhängig vom eingesetzten Polymeren. In der Regel werden die BiOCI-Pigmente in Mengen von 5 - 50 Gew.%, vorzugsweise 10 - 40 Gew.%, insbesondere 10 - 30 Gew.%, bezogen auf die Gesamtmasse, dem Polymeren zugesetzt.However, the use concentration of the BiOCl pigment in shape memory polymers 1 5 depends on the polymers used. As a rule, the BiOCl pigments are added to the polymer in amounts of 5 to 50% by weight, preferably 10 to 40% by weight, in particular 10 to 30% by weight, based on the total mass.
2^ Neben der Funktion als Röntgenkontrastmittel kann das BiOCI-Pigment auch als Füllstoff dienen und damit die Verformbarkeit, Elastizität, Reck- barkeit des Kunststoffes positiv beeinflussen. Sofern das BiOCI-Pigment lediglich als Röntgenkontrastmittel eingesetzt wird, sind die Einsatzkonzentration im Bereich von 5 - 50 Gew.%, vorzugsweise 10 - 40 Gew.%, 2 ^ In addition to the function as x-ray contrast agents can serve the BiOCl pigment as a filler and thus positively influence the deformability, elasticity, stretching bility of the plastic. If the BiOCl pigment is used only as an X-ray contrast agent, the use concentration in the range of 5 to 50 wt.%, Preferably 10 to 40 wt.%,
2^ und ganz besonders bevorzugt 15 - 30 Gew.% bezogen auf die Gesamtmasse des Polymers bzw. der Polymerzubereitung. 2 ^ and most preferably 15 to 30 wt.% Based on the total mass of the polymer or the polymer preparation.
BiOCI-Pigmente sind bekannt, z.B. aus der DE-PS 10 03 377, U.S. 2,975,053, DE 24 11 966, EP 0 496 686 B1 und DE 43 05 280 A1 undBiOCl pigments are known, e.g. from DE-PS 10 03 377, U.S. 2,975,053, DE 24 11 966, EP 0 496 686 B1 and DE 43 05 280 A1 and
^® sind kommerziell erhältlich und werden beispielsweise von der Fa. Merck KGaA, Deutschland unter den Markennamen Bi-Flair®, Biron®, RonaFlair™ sowie von der Fa. BASF unter der Marke Mearlite® angeboten. Die im Handel erhältlichen BiOCI-Pigmente besitzen Teilchengrößen von 1-50 μm. Für den Einsatz der BiOCI-Pigmente in Memory-Shape-Kunststoffe^ ® are commercially available and are, for example, by the company. Merck KGaA, Germany, under the brand name Bi-Flair ®, Biron ®, ™ and RonaFlair by the company. BASF under the brand Mearlite ®. The commercially available BiOCl pigments have particle sizes of 1-50 microns. For the use of BiOCI pigments in memory-shape plastics
3^ sind vorzugsweise BiOCI-Pigmente mit Teilchengrößen von 2-50 μm, insbesondere von 5-20 μm, und ganz besonders bevorzugt von < 15 μm, geeignet. Aufgrund der vielfältigen Produktionsmöglichkeiten sind die platt- chenförmigen BiOCI-Pigmente mit unterschiedlichen optischen Eigenschaften, von matt bis glänzend und von transparent bis hin zu deckend erhältlich. Die Größe der einzelnen Partikel für die stark glänzenden Bi- ^ OCI-Pigmente beträgt vorzugsweise 6-20 μm, insbesondere 8-18 μm und ganz besonders bevorzugt 10-16 μm. 3 ^ are preferably BiOCl pigments having particle sizes of 2-50 .mu.m, in particular 5-20 .mu.m, and most preferably of <15 microns, are suitable. Due to the diverse production possibilities, the flat chenförmig BiOCI pigments with different optical properties, from matt to glossy and from transparent to opaque available. The size of the individual particles for the high-gloss Bi- OCI pigments is preferably 6-20 microns, especially 8-18 microns and most preferably 10-16 microns.
Die BiOCI-Pigmente sind nicht beschichtet, liegen als Plättchen vor und werden als lose Pulver bei der Herstellung des Formgedächtnis-PolymerenThe BiOCl pigments are uncoated, are platelets, and become loose powders in the production of the shape memory polymer
1 ι πu in der Regel dem Monomeren zugesetzt.1 ι π u usually added to the monomer.
Die erfindungsgemäßen Shape-Memory-Polymere werden beispielsweise hergestellt, indem das BiOCI-Pigment in den Kunststoff eincompoundiert wird. Weiterhin kann das BiOCI-Pigment direkt vor bzw. bei der ' ^ Polymerisation des gewählten Kunststoffes in Pulverform zugesetzt und eingemischt werden, so dass ein separates Eincompoundieren vermieden wird. Letztes Verfahren ist bevorzugt, da durch diese schonende Einarbeitung die Plättchenstruktur des BiOCI-Pigments deutlich wenigerThe shape memory polymers according to the invention are prepared, for example, by compounding the BiOCl pigment into the plastic. Furthermore, the BiOCl pigment can be added and mixed directly before or during the polymerization of the selected plastic in powder form, so that a separate compounding is avoided. The latter method is preferred since the platelet structure of the BiOCl pigment is significantly less due to this gentle incorporation
Schaden nimmt. 20Takes damage. 20
Die Herstellung des erfindungsgemäß dotierten Formgedächtnis- Polymeren erfolgt in der Regel so, dass in einem geeigneten Mischer das Kunststoffgranulat vorgelegt, mit eventuellen Zusätzen benetzt und danach das BiOCI-Pigment zugesetzt und untergemischt wird. Dem Kunst-The preparation of the inventively doped shape memory polymer is usually carried out so that presented in a suitable mixer, the plastic granules, wetted with any additives and then the BiOCl pigment is added and mixed. The art
2^ stoffgranulat können bei der Einarbeitung des BiOCI-Pigments gegebenenfalls Haftmittel, organische polymerverträgliche Lösungsmittel, Stabilisatoren und/oder unter den Arbeitsbedingungen temperaturstabile Tenside zugesetzt werden. Die Pigmentierung des Kunststoffes erfolgt in der Regel über ein Farbkonzentrat (Masterbatch) oder Compound. Die so erhaltene 2) granules can be added during the incorporation of the BiOCl pigment optionally adhesives, organic polymer-compatible solvents, stabilizers and / or under the working conditions temperature-stable surfactants. The pigmentation of the plastic usually takes place via a color concentrate (masterbatch) or compound. The thus obtained
30 Mischung kann dann direkt in einem Extruder oder einer Spritzgießmaschine verarbeitet werden. Die bei der Verarbeitung gebildeten Formkörper zeigen eine sehr homogene Verteilung des BiOCI-Pigments.The mixture can then be processed directly in an extruder or an injection molding machine. The shaped bodies formed during processing show a very homogeneous distribution of the BiOCl pigment.
Gegenstand der Erfindung sind auch Formteile, insbesondere für medizin- 3^ technische Produkte, bestehend aus dem erfindungsgemäßen Formgedächtnis-Polymeren enthaltend BiOCI-Pigmente. Die so dotierten Formgedächtnis-Polymere eignen sich insbesondere zur Herstellung von Zahnwurzelkanalstiften, Verstärkungsstiften für die Wirbelsäule, Kathetermaterialien, Gefäßimplantate, z.B. Stents, ^ Implantationshilfsmitteln.The invention also relates to molded parts, in particular for medical 3 ^ technical products comprising the inventive shape memory polymers containing BiOCl pigments. The so-doped shape memory polymers are particularly suitable for the preparation of Zahnrurzelkanalstiften, reinforcing pins for the spine, catheter materials, vascular implants, such as stents, ^ Implantationshilfsmitteln.
In einer bevorzugten Ausführungsform sind die Implantate aus dem erfindungsgemäßen Formgedächtnis-Polymer dergestalt, dass sie mindestens einen medizinischen Wirkstoff, wie z.B. Zytostatika,In a preferred embodiment, the implants of the shape memory polymer of the present invention are such that they contain at least one medicinal agent, e.g. cytostatics,
1 0 antiangiogene Wirksubstanzen, Corticoide, NSAID, Heparin, Hirudin, enthalten, der gegebenenfalls in hoher Konzentration und über einen längeren Zeitraum an das umliegende Gewebe abgegeben wird. Die Wirkstoffe können bei der Polymerisation direkt dem Monomer zugegeben werden und dann im Kunststoffpulver oder Kunststoffgranulat homogen 1 0 antiangiogenic active substances, corticoids, NSAID, heparin, hirudin, which is optionally delivered in high concentration and over a prolonged period to the surrounding tissue. The active ingredients can be added directly to the monomer in the polymerization and then homogeneous in the plastic powder or plastic granules
' ^ verteilt vorliegen oder bei der Verarbeitung der Polyurethanschmelze oder Polyurethanlösung zum Formkörper in gewünschter Menge zugegeben werden. Der bzw. die Wirkstoffe werden bevorzugt im Polymer gelöst oder dispergiert, wobei das Lösen des Wirkstoffs sowohl in der Schmelze als auch in der organischen Lösung des Polymeren durchgeführt werdenBe present distributed or added in the processing of the polyurethane melt or polyurethane solution to the molding in the desired amount. The active ingredient (s) are preferably dissolved or dispersed in the polymer, the dissolution of the active ingredient being carried out both in the melt and in the organic solution of the polymer
^u kann. So kann eine Wirkstoffbeimischung bis zu 30 Gew.% Wirkstoff im Polyurethan erreicht werden. Die Verarbeitung erfolgt wie oben beschrieben durch Extrusion oder Spritzguss, wobei im Extrusions- bzw. Spritzgussverfahren nur thermisch beständige Wirkstoffe verwendet werden können. 25^ u can. Thus, an active ingredient admixture up to 30 wt.% Active ingredient in the polyurethane can be achieved. The processing is carried out as described above by extrusion or injection molding, wherein only thermally stable active ingredients can be used in the extrusion or injection molding process. 25
Gegenstand der vorliegenden Erfindung ist ebenfalls die Verwendung der erfindungsgemäßen radioopaken Formgedächtnis-Polymeren als Implantatwerkstoff, z.B. zur Herstellung von Zahnwurzelkanalstiften, Versteifungsstiften, z. B. für Wirbelsäulen und Rippenknochen, Hüft- und 30 Kniegelenken, zur Herstellung von Knochenzementen, Gefäßimplantaten, Stents, Kathetern, wie z.B. Blasenkatheter, Venenkatheter, zentralvenöse Katheter, Herzkatheter, zur Herstellung von Implantationshilfsmitteln, zur Herstellung von Referenzstiften für verschiedene Anwendungen im Medizinbereich.The present invention also provides the use of the radiopaque shape memory polymers of the invention as an implant material, e.g. for the preparation of dental root canal pins, stiffening pins, z. For spinal and rib bone, hip and knee joints, for the production of bone cements, vascular grafts, stents, catheters, e.g. Bladder catheters, venous catheters, central venous catheters, heart catheters, for the production of implantation aids, for the production of reference pens for various applications in the medical field.
3535
Die nachfolgenden Beispiele sollen die Erfindung näher erläutern, ohne sie jedoch zu begrenzen. Vor- und nachstehend bedeuten Prozentangaben Gewichtsprozent. Alle Temperaturen sind in Grad Celsius angegeben. Beispiele:The following examples are intended to illustrate the invention without, however, limiting it. Above and below, percentages are by weight. All temperatures are in degrees Celsius. Examples:
Beispiel 1 : Herstellung von Kunstoffteilen mittels SpritzgußExample 1: Production of plastic parts by injection molding
Die drei Shape-Memory-Formgedächtniskunststoffe Carbothane® The three shape memory shape memory resins Carbothane ®
- PC 3572D (hart)- PC 3572D (hard)
- PC 3595A (weich) - PC 3555D (mittel)- PC 3595A (soft) - PC 3555D (medium)
der Fa. Lubrizol werden jeweils mit 45 % RonaFlair™ B-50 (BiOCI-Pigment der Teilchengröße 2-35 μm der Fa. Merck KGaA) compoundiert und granuliert. Das Granulat wird in den Trichter der Spritzgießmaschine gefüllt, erwärmt und unter hohem Druck in die Kavitäten des Werkzeuges eingespritzt. Auf diese Weise werdenfrom Lubrizol are each compounded with 45% RonaFlair ™ B-50 (BiOCl pigment particle size 2-35 microns from. Merck KGaA) and granulated. The granules are filled in the hopper of the injection molding machine, heated and injected under high pressure into the cavities of the tool. That way
- Zahnwurzelkanalstifte- Tooth root canal pins
- Stents - Versteifungsstifte- stents - stiffening pins
- Referenzstifte für verschiedene Anwendungen im Medizinbereich- Reference pins for various applications in the medical field
hergestellt.produced.
Die finalen Produkte zeichnen sich durch eine sehr gute Radioopazität aus.The final products are characterized by a very good radio opacity.
Beispiel 2: Herstellung von Kunstoffteilen mittels SpritzgussExample 2: Production of plastic parts by injection molding
Analog Beispiel 1 wird Carbothane PC 3572D (Fa. Lubrizol) mit 40 %Carbothane PC 3572D (Lubrizol) is mixed with 40% as in Example 1.
RonaFlair™ LF-2000 (BiOCI-Pigment der Teilchengröße 2-35 μm der Fa. Merck KGaA) compoundiert und granuliert. Das Granulat wird in den Trichter der Spritzgießmaschine gefüllt, erwärmt und unter hohem Druck in die Kavitäten des Werkzeuges eingespritzt. Auf diese Weise werdenRonaFlair ™ LF-2000 (BiOCl pigment particle size 2-35 microns from Merck KGaA) compounded and granulated. The granules are filled in the hopper of the injection molding machine, heated and injected under high pressure into the cavities of the tool. That way
- Zahnwurzelkanalstifte- Tooth root canal pins
- Stents - Versteifungsstifte- stents - stiffening pins
- Referenzstifte für verschiedene Anwendungen im Medizinbereich- Reference pins for various applications in the medical field
hergestellt.produced.
Die finalen Produkte zeichnen sich durch eine sehr gute Radioopazität aus.The final products are characterized by a very good radio opacity.
Beispiel 3: Herstellung von Kunstoffteilen mittels SpritzgussExample 3: Production of plastic parts by injection molding
Analog Beispiel 1 werden Carbothane PC 3572D (Fa. Lubrizol) mit 45 % RonaFlair™ Fines (BiOCI-Pigment der Teilchengröße 2-35 μm der Fa. Merck KGaA) compoundiert und granuliert. Das Granulat wird in den Trichter der Spritzgießmaschine gefüllt, erwärmt und unter hohem Druck in die Kavitäten des Werkzeuges eingespritzt. Auf diese Weise werdenCarbothane PC 3572D (Lubrizol) is compounded with 45% RonaFlair ™ Fines (BiOCl pigment of particle size 2-35 μm from Merck KGaA) and granulated analogously to Example 1. The granules are filled in the hopper of the injection molding machine, heated and injected under high pressure into the cavities of the tool. That way
- Zahnwurzelkanalstifte- Tooth root canal pins
- Stents . Versteifungsstifte- stents. stiffening pins
hergestellt.produced.
Die finalen Produkte zeichnen sich durch eine sehr gute Radioopazität aus.The final products are characterized by a very good radio opacity.
Beispiel 4: Herstellung von Kathederschläuchen mittels ExtrusionExample 4 Production of Catheter Tubing by Extrusion
Carboethane PC 3572D der Fa. Lubrizol wird 25 % RonaFlair™ B-50 (BiOCI-Pigment der Teilchengröße 2-35 μm der Fa. Merck KGaA) beigemischt und durch Erwärmen in eine zähflüssige Konsistenz überführt und anschließend in einen Extruder gebracht. Die zähe Kunststoffmasse mit verdichtet und durch eine Öffnung zur Formgebung in dasCarboethane PC 3572D from Lubrizol is admixed with 25% RonaFlair ™ B-50 (BiOCl pigment of particle size 2-35 μm from Merck KGaA) and converted by heating to a viscous consistency and then taken to an extruder. The tough plastic compound compacted with and through an opening for shaping in the
Extrusionswerkzeug gepresst. Bei dem Extrusionswerkzeug handelt es sich um ein hohles Werkzeug, in welches die plastische Kunststoffmasse auf der einen Seite durch den Extruder hineingepresst wird, und die es auf der anderen Seite als fertiger Schlauch verlässt. Der Massefluss wird zu diesem Zweck innerhalb des Werkzeugs durch einen Dornhalter aufgespalten und umfließt dabei den Dom, welcher den Hohlraum im Schlauch formt. Während das Schlauchvolumen durch den Dorn bestimmt wird, ist der Durchmesser der Düse durch die der Materialfluss austritt für den äußeren Querschnitt des Schlauchs verantwortlich. Die materialspezifischen Schrumpfungseigenschaften des Kunststoffs bei der Abkühlung beeinflussen die Abmessungen des Endprodukts.Extrusion tool pressed. The extrusion tool is a hollow tool, into which the plastic plastic compound is pressed in on one side through the extruder and leaves it on the other side as a finished tube. The mass flow becomes too this purpose is split within the tool by a mandrel holder and thereby flows around the dome, which forms the cavity in the hose. While the tubing volume is determined by the mandrel, the diameter of the nozzle through which the material flow exits is responsible for the outer cross-section of the tubing. The material-specific shrinkage properties of the plastic during cooling affect the dimensions of the final product.
Das finale Produkt zeichnet sich durch seine ausgezeichnete Röntgenopazität aus. The final product is characterized by its excellent radiopacity.

Claims

Patentansprüche claims
1. Formgedächtnis-Polymere (Shape-Memory-Polymers), dadurch ^ gekennzeichnet, dass sie BiOCI-Pigmente enthalten.1. Shape memory polymers, characterized in that they contain BiOCl pigments.
2. Formgedächtnis-Polymere nach Anspruch 1 , dadurch gekennzeichnet, dass das BiOCI-Pigment plättchenförmig ist.2. Shape memory polymers according to claim 1, characterized in that the BiOCl pigment is platelet-shaped.
10 3. Formgedächtnis-Polymere nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das BiOCI-Pigment Teilchengrößen von 2 -50 μm aufweist. 10 3. Shape memory polymers according to claim 1 or 2, characterized in that the BiOCl pigment has particle sizes of 2-50 microns.
4. Formgedächtnis-Polymere nach einem oder mehreren der Ansprüche '^ 1 bis 3, dadurch gekennzeichnet, dass das BiOCI-Pigment in4. shape memory polymers according to one or more of claims' ^ 1 to 3, characterized in that the BiOCl pigment in
Pulverform eingesetzt wird.Powder form is used.
5. Formgedächtnis-Polymere nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Anteil an BiOCI-Pigment im5. shape memory polymers according to one or more of claims 1 to 4, characterized in that the proportion of BiOCl pigment in
20 Polymeren 5 - 50 Gew.% bezogen auf die Gesamtmasse des 20 polymers 5 - 50 wt.% Based on the total mass of
Polymers bzw. der Polymermischung beträgt.Polymer or the polymer mixture is.
6. Formgedächtnis-Polymere nach einem oder mehreren der Ansprüche6. shape memory polymers according to one or more of the claims
1 bis 5, dadurch gekennzeichnet, dass das Polymer ausgewählt ist aus 2^ der Gruppe der thermoplastischen Kunststoffe.1 to 5, characterized in that the polymer is selected from 2 ^ the group of thermoplastics.
7. Formgedächtnis-Polymere nach einem oder mehreren der Ansprüche7. shape memory polymers according to one or more of the claims
1 bis 6, dadurch gekennzeichnet, dass der thermoplastische Kunststoff ausgewählt ist aus der Gruppe Polyurethan (TPU), Polyester, 30 Polyvinylalkohol, Polyvinylsiloxan, Polycarbonat.1 to 6, characterized in that the thermoplastic material is selected from the group polyurethane (TPU), polyester, 30 polyvinyl alcohol, polyvinylsiloxane, polycarbonate.
8. Formgedächtnis-Polymere nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass sie eine Shore-Härte von 5OA bis 8OD aufweisen. 35 8. shape memory polymers according to one or more of claims 1 to 7, characterized in that they have a Shore hardness of 5OA to 8OD. 35
9. Formgedächtnis-Polymere nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass sie eine Rückstelltemperatur von 35 bis 50 0C aufweisen. 59. shape memory polymers according to one or more of claims 1 to 8, characterized in that they have a reset temperature of 35 to 50 0 C. 5
10. Formgedächtnis-Polymere nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass sie mindestens einen medizinischen Wirkstoff enthalten.10. shape memory polymers according to one or more of claims 1 to 9, characterized in that they contain at least one medicinal agent.
1^ 1 ^
11. Verfahren zur Herstellung von Formgedächtnis-Polymeren nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass man das BiOCI-Pigment in den Kunststoff eincompoundiert oder bei der Polymerisation des gewählten Kunststoffes zugesetzt, und die erhaltene Mischung gegebenenfalls unter Zugabe weiterer Additive in11. A process for the preparation of shape memory polymers according to one or more of claims 1 to 10, characterized in that one compounded the BiOCl pigment in the plastic or added in the polymerization of the selected plastic, and the resulting mixture optionally with the addition of further additives in
' ^ einem Extruder oder in einer Spritzgussmaschine verarbeitet wird.'^ is processed in an extruder or in an injection molding machine.
12. Verfahren zur Herstellung von Formgedächtnis-Polymeren nach Anspruch 11 , dadurch gekennzeichnet, dass man dem Kunststoffpulver oder Compound zusätzlich mindestens einen12. A process for the preparation of shape memory polymers according to claim 11, characterized in that the plastic powder or compound additionally at least one
^u medizinischen Wirkstoff zugibt und die erhaltene Mischung gegebenenfalls unter Zugabe weiterer Additvive in einem Extruder oder in einer Spritzgussmaschine verarbeitet.^ U medicinal active ingredient is added and the mixture obtained is optionally processed in an extruder or in an injection molding machine with addition of further Additvive.
13. Verwendung der Formgedächtnis-Polymere nach einem oder13. Use of shape memory polymers according to one or
2^ mehreren der Ansprüche 1 bis 10 als Knochenzement, zur Herstellung von Wurzelkanalstiften, Versteifungsstiften, Stents, Gefäßimplantate, Kathetermaterialien, Implantationshilfsmitteln, Referenzstifte für Anwendungen in der Medizintechnik. 2 ^ any one of claims 1 to 10 as bone cement, for the production of root canal pins, stiffening pins, stents, vascular grafts, catheter materials, implantation aids, reference pins for applications in medical technology.
30 14. Formkörper bestehend aus einem Formgedächtnis-Polymeren nach einem oder mehreren der Ansprüche 1 bis 10.30 14. Shaped body consisting of a shape memory polymer according to one or more of claims 1 to 10.
35 35
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