(19)
(11)EP 3 280 462 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
06.05.2020 Bulletin 2020/19

(21)Application number: 16718237.7

(22)Date of filing:  07.04.2016
(51)Int. Cl.: 
A61L 27/00  (2006.01)
A61L 24/00  (2006.01)
C08L 71/08  (2006.01)
A61F 2/28  (2006.01)
C08K 5/00  (2006.01)
(86)International application number:
PCT/EP2016/057631
(87)International publication number:
WO 2016/162427 (13.10.2016 Gazette  2016/41)

(54)

RADIOOPAQUE PEEK BASED BLOCK FOR USE IN A CAD/CAM SYSTEM FOR THE MANUFACTURE OF A DENTAL RESTAURATION

RÖNTGENUNDURCHLÄSSIGER BLOCK AUF PEEK-BASIS ZUR VERWENDUNG IN EINEM CAD/CAM-SYSTEM ZUR HERSTELLUNG EINER ZAHNRESTAURATION

BLOC À BASE DE PEEK RADIO-OPAQUE POUR SON UTILISATION DANS UN SYSTÈME CAD/CAM POUR LA FABRICATION D'UNE RESTAURATION DENTAIRE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 07.04.2015 FR 1552949

(43)Date of publication of application:
14.02.2018 Bulletin 2018/07

(73)Proprietor: Société de Recherches Techniques Dentaires - R.T.D.
38120 Saint Egrève (FR)

(72)Inventors:
  • REYNAUD, Pierre-Luc
    38410 Vaulnaveys le Haut (FR)
  • CHU, Manh-Quynh
    38120 Fontanil Cornillon (FR)
  • LIM, Hyung Sup
    Ansan-City (KR)
  • LIM, Hyung Jun
    Anyang-City (KR)
  • YOO, Young Cheol
    Ansan-City (KR)

(74)Representative: Cabinet Laurent & Charras 
Le Contemporain 50 Chemin de la Bruyère
69574 Dardilly Cedex
69574 Dardilly Cedex (FR)


(56)References cited: : 
WO-A1-96/03161
US-A1- 2006 052 479
WO-A2-2006/127838
US-A1- 2011 270 407
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description


    [0001] The invention pertains to thermoplastic polymers materials used in particular in the field of dentistry. It more especially concerns a block consisting of a thermoplastic polymer for use in a CAD/CAM system for the manufacture of a dental restauration.

    [0002] Polymers such as PMMA, PE, or even PEEK are an ideal alternative as substitute materials of metallic or ceramic materials. Thus, they can be used for spinal, orthopedic or dental implants. They offer many advantages such as an absence of interferences with scanners, a biomechanical behavior similar to that of bone, a proved biocompatibility... The preferred biocompatible polymer is PEEK (Polyether Ether Ketone), a thermoplastic polymer.

    [0003] However, these polymers are unfortunately non radiopaque to X-rays. They are hardly detected when used in spinal, orthopedic or dental implants. Moreover, it is also difficult to detect their localisation when used in dental restorative materials, for instance, in case of accidental ingestion.

    [0004] Documents US 2011/0270407 and US2006/0052479 disclose a medical or veterinary material, an implant, which could comprise charges such as TiO2, ZrO2, Al2O3 and SiO2. Document WO 2006/127838 discloses prosthetic dental devices comprising PEEK which comprise ceramic fillers selected from yttria-stabilized zirconia, magnesium-stabilized zirconia, alumina, titanium dioxide, calcium phosphates

    [0005] To the applicant's knowledge and to avoid this drawback, there is nowadays only one radiopaque PEEK polymer made with barium sulfate (BaSO4) fillers. This compound is a white solid oxide, usually highly pure, used as an opacifier in paintings or as "boiled barium" in medical radiology, particularly for gastrointestinal tract monitoring.

    [0006] Although such filled polymers have radio-opacity property, the radio opacity level remains quite low making them difficult to be detected, unless the fillers concentration is increased significantly. However, such concentration may cause final material having lower final mechanical properties. In addition, its high refractive index together with the large size of particles leads to a final product which is opaque to light or has a diminished aesthetic appearance. As already said, filled polymers have lower mechanical properties than unfilled polymers.

    [0007] This present invention relates to a thermoplastic polymer material selected from the group comprising PEEK including radiopaque particles selected from the group comprising BaZrO3, YbF3, Yb2O3, SrO, SrZrO3, SiO2-ZrO2, SiO2-Yb2O3, Lu2O3, LuF3.

    [0008] Particles are incorporated into the polymer by grafting or incorporation methods. In practice, the polymer is formed as pellet-like.

    [0009] As above explained, metallic oxydes, most particularly, heavy metals or rare earths compounds, barium sulfate, carbonates, are well-known to confer radiopaque properties to polymer-based composite materials. Particles are mixed together with the resin and the remainder material components during the manufacturing.

    [0010] Preferred particles of the invention are selected from barium zirconate (BaZrO3), ytterbium fluorure (YbF3), ytterbium oxide (Yb2O3) and a combination thereof for biocompatibility, implementation (dispersion, mechanical, optical (transparency), and cost reasons.

    [0011] Radiopaque compounds consist of particles having preferably a spherical, rod-like or any other shapes. These particles may be functionnalised as well. Particles size is lower than 1 µm, preferably ranging from 0,2 to 0,9 µm.

    [0012] In another embodiment, particles represent at least 2% by weight of total polymer weight.

    [0013] MMA-based (Méthyl Méthacrylate) is the preferred component for functionalizing these particles due to its structure which makes easier its incorporation into PEEK.

    [0014] Thus, radiopaque polymer formed can be used as medical implant material such as spinal, orthopedic, dental implants or dental block CAD CAM. It may also be used as polymeric matrix of a reinforced-fibers composite material in dental post, abutments applications...

    [0015] In an embodiment, the invention concerns a block for use in a CAD/CAM system for the manufacture of a dental restauration, said block consisting of a thermoplastic polymer comprising PEEK including radiopaque particles selected from the group comprising BaZrO3, YbF3, Yb2O3, SrO, SrZrO3, SiO2-ZrO2, SiO2-Yb2O3, Lu2O3, LuF3.

    [0016] Advantageously, radiopaque particles are selected among YbF3, Yb2O3 or LuF3, Lu2O3.

    [0017] The blocks of the invention are deprived of calcium and phosphates.

    [0018] In some embodiments, the block contains pigments as coloring agent.

    [0019] As dental restauration, the invention covers crowns, brides, abutments, bars....

    [0020] Many other embodiments may be possible for someone with ordinary skills in the art.

    [0021] In practice, radiopaque polymer pellets are first ground and then cooled depending on the applications.

    Examples



    [0022] The goal of this example is to study the radiopacity of a block made of PEEK including Yb2O3

    Material:



    [0023] 

    Sample A: PEEK

    Sample B: PEEK 12% Yb2O3

    Sample C: PEEK 24% Yb2O3


    Method:



    [0024] The method corresponds to that disclosed in ISO 4049.
    The sample are square having a length of around 5 mm and a thickness of 1±0.1mm
    5 density measurements are made by sample. Measurements correspond to an equivalency of thickness of aluminium and then is divided by the thickness for obtaining the equivalency of 1 millimeter of material by aluminum millimeter.

    [0025] Sample A is not radiopaque. Samples B and C have a percentage aluminium equivalent of 113% and 303% and are both radiopaque.


    Claims

    1. Thermoplastic polymer material comprising PEEK including radiopaque particles selected from the group comprising BaZrO3, YbF3, Yb2O3, SrO, SrZrO3, SiO2-ZrO2, SiO2-Yb2O3, Lu2O3, LuF3.
     
    2. Thermoplastic polymer material according to claim 1, wherein radiopaque particles are selected among YbF3, Yb2O3.
     
    3. Thermoplastic polymer material according to claim 1, wherein radiopaque particles are selected among LuF3, Lu2O3.
     
    4. Thermoplastic polymer material according to one of the preceding claims, wherein particles size is lower than 1 µm, preferably ranging from 0,2 µm to 0,9 µm.
     
    5. Thermoplastic polymer material according to one of the preceding claims, wherein particles represent at least 2% by weight of total polymer weight.
     
    6. Thermoplastic polymer material according to one of the preceding claims, wherein said polymer is pellet-like.
     
    7. Thermoplastic polymer material according to claims 1 to 6 wherein it includes pigments.
     
    8. Use of the thermoplastic polymer material according to one of the preceding claims as a medical implant material selected from the group consisting of spinal, orthopedic and dental implants.
     
    9. Use of the thermoplastic polymer material according to claims 1 to 7, as polymeric matrix of a reinforced-fibers composite material in dental post or abutments applications.
     
    10. Use of the thermoplastic polymer material according to claims 1 to 7, as a block in a CAD/CAM system for the manufacture of dental restoration.
     
    11. Use according to claim 10, wherein dental restoration is crown, bridge, abutment, bar.
     


    Ansprüche

    1. Thermoplastisches Polymermaterial, das PEEK enthält, mit röntgenundurchlässigen Teilchen, die zur Gruppe mit BaZrO3, YbF3, Yb2O3, SrO, SrZrO3, SiO2-ZrO2, SiO2-Yb2O3, Lu2O3, LuF3 gehören.
     
    2. Thermoplastisches Polymermaterial gemäß Anspruch 1, wobei die röntgenundurchlässigen Teilchen aus YbF3 oder Yb2O3 ausgewählt werden.
     
    3. Thermoplastisches Polymermaterial gemäß Anspruch 1, wobei die röntgenundurchlässigen Teilchen aus LuF3 oder Lu2O3 ausgewählt werden.
     
    4. Thermoplastisches Polymermaterial gemäß einem der vorangehenden Ansprüche, wobei die Teilchengröße kleiner ist als 1 µm und am Besten im Bereich zwischen 0,2 µm und 0,9 µm liegt.
     
    5. Thermoplastisches Polymermaterial gemäß einem der vorangehenden Ansprüche, wobei die Teilchen mindestens 2 Gewichts-% des gesamten Polymergewichtes darstellen.
     
    6. Thermoplastisches Polymermaterial gemäß einem der vorangehenden Ansprüche, wobei das genannte Polymer granulatähnlich ist.
     
    7. Thermoplastisches Polymermaterial gemäß einem der Ansprüche 1 bis 6, wobei es Pigmente enthält.
     
    8. Verwendung des thermoplastischen Polymermaterials gemäß einem der vorangehenden Ansprüche als medizinisches Implantatmaterial, das aus der Gruppe ausgewählt wird, die aus spinalen, orthopädischen und Dentalimplantaten besteht.
     
    9. Verwendung des thermoplastischen Polymermaterials gemäß einem der vorangehenden Ansprüche 1 bis 7, als Polymermatrix eines faserverstärkten Verbundmaterials bei dentalen Implantataufbau- oder Brückenpfeiler-Anwendungen.
     
    10. Verwendung des thermoplastischen Polymermaterials gemäß einem der vorangehenden Ansprüche 1 bis 7, als Block in einem CAD/CAM- System zur Herstellung einer Zahnrestauration.
     
    11. Verwendung gemäß Anspruch 10, wobei es sich bei der Zahnrestauration um eine Krone, Brücke, Brückenpfeiler oder Steg handelt.
     


    Revendications

    1. Matériau polymère thermoplastique comprenant du PEEK et des particules radio-opaques choisies dans le groupe comprenant BaZrO3, YbF3, Yb2O3, SrO, SrZrO3, SiO2-ZrO2, SiO2-Yb2O3, Lu2O3, LuF3.
     
    2. Matériau polymère thermoplastique selon la revendication 1, caractérisé en ce que les particules radio-opaques sont choisies dans le groupe YbF3, Lu2O3.
     
    3. Matériau polymère thermoplastique selon la revendication 1, caractérisé en ce que les particules radio-opaques sont choisies dans le groupe LuF3, Lu203.
     
    4. Matériau polymère thermoplastique selon l'une des revendications précédentes, caractérisé en ce que les particules sont de taille inférieure à 1 µm, de préférence comprise entre 0,2 µm et 0,9 µm.
     
    5. Matériau polymère thermoplastique selon l'une des revendications précédentes, caractérisé en ce que les particules représentent au moins 2 % en poids du poids total du polymère.
     
    6. Matériau polymère thermoplastique selon l'une des revendications précédentes, caractérisé en ce que ledit polymère se présente sous la forme de granules.
     
    7. Matériau polymère thermoplastique selon les revendications 1 à 6, caractérisé en ce qu'il comprend des piments.
     
    8. Utilisation du matériau polymère thermoplastique selon l'une des revendications précédentes, comme matériau d'implants médicaux choisi dans le groupe constitué par les implants rachidiens, orthopédiques et dentaires.
     
    9. Utilisation du matériau polymère thermoplastique selon les revendications 1 à 7, comme matrice polymérique d'un matériau composite renforcé par des fibres dans les applications telles qu'un tenon dentaire ou un pilier d'implant.
     
    10. Utilisation du matériau polymère thermoplastique selon les revendications 1 à 7, comme bloc pour usinage par CFAO pour la fabrication de restauration dentaire.
     
    11. Utilisation selon la revendication 10, caractérisée en ce que la restauration dentaire est une couronne, un bridge, un pilier d'implant ou une barre.
     




    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description