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WO1993007911A1 - Elements biocompatible a implanter - Google Patents

Elements biocompatible a implanter Download PDF

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Publication number
WO1993007911A1
WO1993007911A1 PCT/JP1992/001341 JP9201341W WO9307911A1 WO 1993007911 A1 WO1993007911 A1 WO 1993007911A1 JP 9201341 W JP9201341 W JP 9201341W WO 9307911 A1 WO9307911 A1 WO 9307911A1
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WO
WIPO (PCT)
Prior art keywords
bioimplant
hydroxyapatite
featuring
resin
elements described
Prior art date
Application number
PCT/JP1992/001341
Other languages
English (en)
Inventor
Tadashi Kokubo
Original Assignee
Tadashi Kokubo
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 Tadashi Kokubo filed Critical Tadashi Kokubo
Publication of WO1993007911A1 publication Critical patent/WO1993007911A1/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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/32—Phosphorus-containing materials, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00389—The prosthesis being coated or covered with a particular material
    • A61F2310/00592—Coating or prosthesis-covering structure made of ceramics or of ceramic-like compounds
    • A61F2310/00796—Coating or prosthesis-covering structure made of a phosphorus-containing compound, e.g. hydroxy(l)apatite

Definitions

  • the present invention concerns bioimplant elements to be used for life support or treatment in case of illness or accidents. That is, it is related to an element which is located at the connection between inside and outside a body to externally provide liquid medicine through a catheter, etc., a bioimplant element which is totally implanted in vivo to provide an injection port for injecting medicine deep inside the body, or a bioimplant element which is to replace or supplement damaged parts of hard structures such as bones.
  • the electrophoresis process can be applied only to metallic base materials with good electrical conductivity because it uses the base material itself as electrodes and also forms coating of apatite which is different from the apatite in vivo because it uses crystal apatite as the source material.
  • the present invention is the result of the concentrated efforts by its inventor to resolve the various problems described above, more specifically, the problem in (F) . It is intended to provide bioimplant elements of organic polymer base which have excellent biological compatibility, sufficient strength and design flexibility.
  • the bioimplant element pertaining to the present invention features hydroxyapatite coating formed on the surface of the base material in a practically saturated or supersaturated water solution of hydroxyapatite, more preferably in an artificial body fluid with the same ion type and concentration as the human blood plasma, where the base material is selected from polymers containing esters in the principal or/and side chains or polymers containing hydroxyl group in the side chains or/and at the end of the chain.
  • bioimplant element More specific characteristics of the said bioimplant element include the following.
  • the desirable thickness of hydroxyapatite is in the range of 3 - IOOIUI
  • the effective organic polymer containing esters in the principal chain can be selected from among allyl resi r oxybenzoyl polyester, polyacrylate, polybutylene terephthalate, polycarbonate or polyethylene terephthalate.
  • the effective organic polymer containing esters in the side chains can be selected from among AAS resin (acrylic ester-acrylonirile-stylrene copolymer) , cellulosic plastics such as cellulose acetate, cellulose butyrate and ethylene cellulose, ethylene- acrylic ester copolymer, acrylic ester-butadien-styrene copolymer, methacrylic resin, or vinyl acetate resin.
  • AAS resin acrylic ester-acrylonirile-stylrene copolymer
  • cellulosic plastics such as cellulose acetate, cellulose butyrate and ethylene cellulose, ethylene- acrylic ester copolymer, acrylic ester-butadien-styrene copolymer, methacrylic resin, or vinyl acetate resin.
  • the desirable organic polymer containing hydroxyl group in the side chains or/and at the end of the chain can be selected from epoxy resin, phenol resin, or polyvinyl alcohol.
  • Nonspecular surface of the base material is particularly effective.
  • a part of phosphate group or hydroxyl group in hydroxyapatite has been substituted by carbonic group.
  • CaO/SiO_ base glass powder has grain diameters in the range of 100 - 600 urn .
  • an organic polymer for the base material of the bioimplant element must be selected from polymers containing esters in the principal chain or/and the side chains or polymers containing hydroxyl group in the side chains or/and at the end of the chain in order to obtain sufficient bonding strength with hydroxyapatite for practical use.
  • the organic polymer containing esters in the principal chain can be selected from among allyl resin, oxybenzoyl polyester, polyacrylate, polybutylene terephthalate, polycarbonate or polyethylene terephthalate.
  • other polymers may be used satisfactorily for the purpose of the present invention as long as sufficient esters are contained in the principal chain.
  • the organic polymer containing esters in the side chains can be selected from among AAS resin (acrylic ester-acrylonitrile-styrene copolymer) , cellulosic plastics such as cellulose acetate, cellulose butyrate and ethylene cellulose, ethylene-vinylacetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, methacrylic resin, or vinyl acetate resin.
  • AAS resin acrylic ester-acrylonitrile-styrene copolymer
  • cellulosic plastics such as cellulose acetate, cellulose butyrate and ethylene cellulose, ethylene-vinylacetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, methacrylic resin, or vinyl acetate resin.
  • other polymers may be used satisfactorily for the purpose the present invention as long as sufficient esters are contained in the side chains.
  • the organic polymer containing hydroxyl group in the side chains or/and at the end of the chain can be selected from epoxy resin, phenol resin or polyvinyl alcohol, however, other organic polymers may be satisfactorily used for the purpose of the present invention as long as sufficient hydroxyl group is contained in the side chains or/and at the end of the chain .
  • polyvinyl alcohol In the case of polyvinyl alcohol, it must be in the partially bridged form so that it is insoluble in water. Otherwise its function as a bioimplant element cannot be achieved.
  • the desirable thickness of hydroxyapatite coating is in the range of 3-100z-m.
  • the thickness of coating is below 3,um it may possibly be eroded and eliminated while implanted in a living body.
  • it exceeds 100 zzm strains caused by the differences in expansion coefficients between the base material and hydroxyapatite against temperature and humidity changes tend to be excessive and as a consequence the hydroxyapatite coating becomes more susceptible to cracking and subsequent separation which develops from such cracks.
  • the increased time to formation of such thick coating of hydroxyapatite inflates the manufacturing costs, making the thickner coating unpracticable.
  • the preferable hydroxyapatite is that with a part of its phosphate or hydroxyl group substituted by carbonic group, because in such form it is closer to hydroxyapatite in a living body and has better biological compatibility.
  • the Ca0/Si0 base glass powder refers to the glass powder which contains CaO and i0 2 in the following ranges.
  • the preferred grain diameter of the glass powder is in the range of 100 - 600um. If it is below 100 xim, it is too small for sufficient amount of saturated or supersaturated water solution .of hydroxyapatite to be supplied between glass grains and the base material and the growth of the hydroxyapatite coating does not occur or is too slow to be practicable. If, on the other hand, it exceeds 600um, sufficient nuclei for growth are not formed on the surface of the base material and therefore the growth is too slow or the surface becomes nonuniform, making it unpracticable. In addition, it is desirable that more than 80% of the glass powder has grain diameters in the range of 100 - 600 xtm. If it is below 80%, the increase in grains having diameters not in the range of 100 - 600 m retards the growth of hydroxyapatite or totally prevents its growth.
  • Fig. 1 Configuration of the bioimplant element used in embodiments of the present invention.
  • FIG. 2 Schematic of first process of hydroxyapatite coating in the present invention.
  • FIG. 3 Schematic of second process of hydroxyapatite coating in the present invention.
  • FIG. 4 An implant device assembled using the bioimplant element of the present invention.
  • FIG. 5 Illustration of the bioimplant element in Fig. 4 implanted in a living body.
  • the CaO/SiO- base glass used in the present invention was prepared from the compound of glass materials shown in the left column below. The composition of the glass obtained is shown in the right column.
  • the uniformly mixed fine powder obtained from the compound of glass materials shown above using a mortar was melted for 2 hours at 145°C in a platinum crucible. It was rapidly quenched on a steel plate and then milled in a ballmill. This was then shifted to prepare several glass powders classified in Table 1. These 4 glass samples were used in the evaluation.
  • FIG. 1 shows the configuration of the implant element called a skin button
  • Figures 2 and 3 which are schematics of the process of hydroxyapatite coating on the surface of the implant element.
  • 11 is the implant element made of polyethersulfon (ICI Co. brand name: PES4100G) ,
  • 1 is the top adapter
  • 2 is the bottom adapter which is connected to the flange 3 of the top adapter 1 and connects the vents 8 and 8a via the vent 8b.
  • 4 and 4a are the vessel, 5 is the glass powder described above, 6 is Solution(l) , and 7 is Solution (2).
  • hydroxyapatites coating (not shown in the figure) of the present invention similar to bones is formed on the surface of the implant element 11 which is in contact with the glass powder 5, as shown in Figure 1.
  • Total 22 samples consisting of 11 embodiments and 11 references were prepared through the procedure described above. Two elements were prepared for each sample condition and one was used for breaking test and the other was implanted in a grown dog to evaluate biological compatibility. The following three characteristics, A - C, were evaluated.
  • a part of the flange of the said implant element was cut off and a cellophane tape (adhesive tape ) was put on undamaged part of coating.
  • the bonding strength was evaluated by observing whether separation of the hydroxyapatite coating occurs when the tape was peeled off.
  • the implant device shown in Figure 4 was assembled using the said implant element which was not used in the breaking test.
  • the device sterilized with ethylene oxide gas was implanted in the breast of a grown dog, as shown Figure 5.
  • the biological compatibility was evaluated observing the conditions after 1 day, 3 days, 1 week, 2 weeks, 3 weeks and 1 month.
  • the implant device was partially implanted in the body. The evaluation was made by observing the conditions at the interface between the skin surface and the implant device.
  • the upper type 12 is connected to the vent 8 of the implant element 11 and the lower tube 13 is connected to the vent 8a by the tightening thread 14.
  • a uer adapter 17 and an intermittent infusion plug 18 are attached and fixed with a clamp 19.
  • the bottom adapter 2 including the flange 3 the implant element 11 is implanted under the skin, namely is inside the body and the end of the lower tube 13 is connected to the inserted catheter 16 via the connector 15 and extended to the prescribed organ (not shown) in the body.
  • Embodiments 1 - 3, Embodiment 4 and Embodiment 5 - 10 in comparison with the reference samples.
  • Embodiments 1 - 3 are identical to Embodiments 1 - 3 :
  • Embodiments 1 - 3 it is shown that the implant elements base on the present invention can be bonded to hydroxyapatite coating with more than adequate strength for practical use and have excellent biological compatibility.
  • the embodiments were prepared varying the base material and the glass, as presented in Table 2 along with the results of evaluation.
  • the base materials used in the reference samples are polystyrene, polypropylene, Teflon, ABS resin, polyvinyl chloride resin, polyurethane resin and nylon.
  • the specifications of References 1 - 10 and the results of evaluation are presented in Table 3.
  • Polymethyl methacrylate base material in Reference 1 was the same as that in Table 7 of Embodiment 2 in Tokkai Hei 2 (1990) - 25515, but Ca0/Si0 2 base glass sheets with the same composition as the glass powder were immersed in Solution (1) at intervals of 0.5 mm.
  • Polyethylene base material in Reference 2 was prepared in the same conditions as those in Table 7 of Embodiment 2 in Tokkai Hei 2 (1990) - 25515. Ca0/Si0 2 base glass sheets were immersed in Solution (1) at intervals of 0.5mm along with the base material.
  • Polyethylene base material in Reference 3 was prepared in the same conditions as those in Table 7 of Embodiment 2 in Tokkai Hei 2(1990) - 25515, which was immersed in Solution (1) along with the same Ca0/Si0 2 base glass powder as that used in Embodiment 1. The surfaces of all base materials were made rough using #150 sand paper.
  • the bioimplant elements in Embodiment 2 were prepared in the following procedure.
  • the injection molded bioimplant elements made of Denkastyrol MW in the same shape as those in Embodiment 1 were dipped twice in the solution described below, cooled at -5 C and gelled by crystallizing- polyvinyl alcohol.
  • the samples were then annealed in silicone oil to be coated with a transparent hydro gel containing less than 20% water.
  • the bioimplant elements thus prepared were then coated with hydroxyapatite in the same procedure as in Embodiment 1.
  • the downgrowth shown in Tables 2 and 3 refers to the phenomenon that the skin sinks around the interface with the implant element when their biological compatibility is poor.
  • the biological compatibility is judged to be better when there is less downgrowth. It is believed that, when the biological compatibility is good, the resistance of the organism against external infectants does not decrease and that therefore the infection does not readily develop.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • Embodiment 4 it is demonstrated that it is desirable for more than 80% of the glass powder to have grain diameters in the range of 100 - 600 urn.
  • Embodiments 5 - 10 are identical to Embodiments 5 - 10:
  • Embodiments 5 - 10 were prepared by changing only the duration of immersion of the implant elements in Solution (2) to obtain different thicknesses of hydroxyapatite coating. Other conditions were the same as those in Embodiment 1. The specifications of the embodiments and the results of evaluation are present in Table 5.
  • Embodiment 11 is a diagrammatic representation of Embodiment 11:
  • the implant base material made of polyethylene terephthalate manufactured by Tokyo Rayon in the shape of a circular cylinder with a radius 8mm and a height 15mm was coated with 14mm thick hydroxyapatite in a manner similar to that in Embodiment 1.
  • This element was implanted in a thighbone of a rabbit. It was removed after 10 weeks and the bonding conditions between the implant element and the bone were examined. It was observed that living tissue was totally united with the implant element.
  • hydroxyapatite exhibits excellent biological compatibility. Nevertheless, because of its low strength, its use for implant elements in the form of the sintered hydroxyapatite has been limited to the parts not subjected to large loads. While metallic base materials or processes of coating ceramics have been developed to overcome this difficulty, they have not been used for general purpoose implant elements because the materials are expensive or have poor moldability. Naturally it is ideal to coat organic polymers, which have much better moldability and are less expensive than other materials, with hydroxyapatite. However, this has not been practicable because the bonding strength with hydroxyapatite has not been sufficient.
  • the present invention creates bioimplant elements with bone-like hydroxyapatite coating on the surface of organic polymer base materials containing esters in the principal chain or/and the side chains or hydroxyl group in the side chains or/and at the end of the chain using practically saturated or supersaturated water solution of hydroxyapaties.
  • the bioimplant elements thus obtained have excellent biological compatibility, sufficient strength and design flexibility, and its significant contributions to medical field are expected.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Transplantation (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Inorganic Chemistry (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Materials For Medical Uses (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Eléments biocompatibles à implanter dotés d'un revêtement en hydroxyapatite dont la structure et la composition sont semblables à celles des os, ce revêtement étant déposés sur un matériau de base en polymère organique. Chaque élément à implanter (1) est constitué d'un matériau de base en polymère organique contenant des esters dans la chaîne principale et/ou dans les chaînes latérales, ou un groupe hydroxyle dans les chaînes latérales et/ou en fin de chaîne. La surface de la partie à implanter, notamment celle del'adaptateur supérieur (1), de la bride (3) et de l'adaptateur inférieur (2), est revêtue d'hydroxyapatite dont la structure et la composition sont semblables à celles des os.
PCT/JP1992/001341 1991-10-15 1992-10-15 Elements biocompatible a implanter WO1993007911A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP3266017A JPH1133106A (ja) 1991-10-15 1991-10-15 生体インプラント部材
JP3/266017 1991-10-15

Publications (1)

Publication Number Publication Date
WO1993007911A1 true WO1993007911A1 (fr) 1993-04-29

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PCT/JP1992/001341 WO1993007911A1 (fr) 1991-10-15 1992-10-15 Elements biocompatible a implanter

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JP (1) JPH1133106A (fr)
AU (1) AU3230093A (fr)
WO (1) WO1993007911A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE526749C2 (sv) 2003-12-11 2005-11-01 Nobel Biocare Ab Anordning vid dentalt implantat samt förfarande för dess framställning
EP3034033A1 (fr) 2014-12-16 2016-06-22 Nobel Biocare Services AG Implant dentaire
CN117562686A (zh) 2018-11-12 2024-02-20 诺贝尔生物服务公司 牙科植入物、用于牙科应用的部件、用于形成保护层的方法和具有保护层的可植入部件

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0389713A1 (fr) * 1989-03-29 1990-10-03 Kyoto University Procédé de revêtement avec une pellicule d'hydroxyapatite bioactive

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0389713A1 (fr) * 1989-03-29 1990-10-03 Kyoto University Procédé de revêtement avec une pellicule d'hydroxyapatite bioactive

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Publication number Publication date
JPH1133106A (ja) 1999-02-09
AU3230093A (en) 1993-05-21

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