WO1993007916A2 - Element d'implant corporel bioactif, recouvert d'une couche d'apatite - Google Patents

Element d'implant corporel bioactif, recouvert d'une couche d'apatite Download PDF

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Publication number
WO1993007916A2
WO1993007916A2 PCT/US1992/008640 US9208640W WO9307916A2 WO 1993007916 A2 WO1993007916 A2 WO 1993007916A2 US 9208640 W US9208640 W US 9208640W WO 9307916 A2 WO9307916 A2 WO 9307916A2
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WO
WIPO (PCT)
Prior art keywords
hydroxyapatite
body implant
implant component
substrate
further characterized
Prior art date
Application number
PCT/US1992/008640
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English (en)
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WO1993007916A3 (fr
Inventor
Masaki Ogawa
Original Assignee
Sherwood Medical Company
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 Sherwood Medical Company filed Critical Sherwood Medical Company
Publication of WO1993007916A2 publication Critical patent/WO1993007916A2/fr
Publication of WO1993007916A3 publication Critical patent/WO1993007916A3/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
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/446—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46
    • 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
    • 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
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/443—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with carbon fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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 a component which is located at an interface between the inside and outside of a human body in a case where life-sustaining or therapeutic chemical solutions are administered from outside the body via catheters, etc. in times of diseases or accidents, a body implant component which is completely buried into a body and which serves as a dispensing port in a case where a chemical solution is administered to areas deep inside the body, and a body implant component which replaces or repairs missing hard tissues (e.g., bones, etc.).
  • a body implant component which is completely buried into a body and which serves as a dispensing port in a case where a chemical solution is administered to areas deep inside the body
  • a body implant component which replaces or repairs missing hard tissues (e.g., bones, etc.).
  • Japanese Patent Disclosure No. To kai Hei 3[1991]186272 notes a bone implant component which is obtained by coating a calcium phosphate material (e.g., hydroxyapatite, etc.) on a ceramic material (e.g., alumina, zirconia, etc.), pure titanium, titanium alloys, etc.
  • a calcium phosphate material e.g., hydroxyapatite, etc.
  • a ceramic material e.g., alumina, zirconia, etc.
  • Japanese Patent Application Publication No. Kokai Hei 2[1990]13580 notes a method wherein a body terminal consisting of a sintered hydroxyapatite is used in a component which lines the inside and outside of a body in a case where the information inside the body is retrieved on the outside.
  • Japanese Utility Model Application Publication No. Jikkai Hei 3[1991]-19884 notes a technique concerning an hydroxyapatite body terminal consisting of organic bones.
  • Japanese Patent Disclosure No. Tokkai Hei 3[1991]-32676 notes a technique regarding a composite consisting of zirconia or alumina and hydroxyapatite in order to improve the low strength of the hydroxyapatite, which has precluded its practical applications.
  • Japanese Patent Application Publication No. Kokai Hei 2[1990]-13580 notes a sintering method.
  • a method for plasma spraying a metal implant is shown in Japanese Patent Application Publication No. Kokai Sho 58[1983]-50737.
  • Methods for plasma-melt spraying ceramic core materials are mentioned in Japanese Patent Application Publication No.
  • body implant components especially bioactive apatite film-coated body implant components
  • manufacturing methods have many problems, as will be illustrated in A through F below.
  • a substrate is used as an electrode, and accordingly, only metal substrates with high electric conductivity can be used. Since a sintered apatite is used as a feed material, an apatite film different from the apatite inside the body is formed.
  • the objective of the present invention which has been proposed as a result of exhaustive research by the present inventors for solving the aforementioned problems (especially the problem of F) , is to provide a body implant component with a high design freedom which exhibits an excellent body compatibility and which has sufficiently high strengths.
  • the bioactive apatite film-coated body implant component of the present invention is a body implant component which is obtained by immersing a body implant component substrate which possesses a surface adhesive layer in an aqueous hydroxyapatite solution with a virtually saturated or supersaturated concentration for the purpose of forming a bone-analogous hydroxyapatite film on the surface of said substrate.
  • Said adhesive layer is a composite which consists principally of an organic polymer with a high affinity for the substrate and an inorganic filler powder the weight ratio of which is 1-30 with respect to said organic polymer and at least 80 wt% of which is accounted for by particles with sizes of 3-100 ⁇ m.
  • the following several mechanisms are effective for accomplishing the aforementioned objective. It is desirable that the thickness of the hydroxyapatite film formed on the substrate surface be 3-100
  • inorganic fillers include barium sulfate, lead sulfate, barium carbonate, calcium carbonate, silicon dioxide, bismuth tungstenate, glass powder consisting principally of CaO and SiO: , and mixtures consisting principally of the foregoing materials. It is desirable that the substrate and organic polymer be composed of an identical material. Moreover, it is desirable that the average dry film thickness of said organic polymer, which contains an inorganic filler and which exhibits an excellent adhesive strength with the substrate, be 5100 m.
  • Figure 1 shows a top view of a bioimplant element on which hydroxyapatite may be coated according to the present invention.
  • Figure 2 shows a sectional side view of the bioimplant element shown in Figure 1.
  • Figure 3 shows a right side view of the bioimplant element shown in Figure 2.
  • Figure 4 shows a schematic representation of one step in the preferred process for hydroxyapatite coating according to the present invention.
  • Figure 5 shows a schematic representation of another step in the preferred process for hydroxyapatite coating according to the present invention.
  • Figure 6 shows an implant device assembled using the bioimplant element shown in Figures 1-3 according to the present invention.
  • Figure 7 is an illustration of the bioimplant device shown in Figure 6 implanted in a living body.
  • the substrate is immersed in an "organic polymer solution which exhibits an excellent adhesive strength with the substrate" and which contains an "inorganic filler powder at least 80 wt% of which is characterized by diameters of 3-100 ⁇ m" and the weight ratio of which is 1-30 with respect to the organic polymer (in a dry state) , and after said substrate has been immersed in an aqueous component solution [sic] with a virtually saturated or supersaturated concentration, a bone-analogous hydroxyapatite film is formed on the substrate surface.
  • the inorganic filler it is necessary that at least 80 wt% of the inorganic filler be characterized by diameters of 3-100 ⁇ m.
  • the particle size distribution is limited to 3-100 ⁇ m for the following reasons. If the particle size is smaller than 3 ⁇ m, the particles are buried into the organic polymer film, which serves as an inorganic filler binder, and as a result, it becomes impossible to firmly fix the hydroxyapatite. If the size exceeds 100 ⁇ m, the binder organic polymer film can no longer hold said inorganic filler fixed to the substrate. Even if the hydroxyapatite is firmly fixed, therefore, the substrate and inorganic filler are peeled off one another, which is unacceptable from a practical point of view.
  • the ratio of the inorganic filler with sizes of 3-100 ⁇ is must be maintained at 80 wt% or higher since it becomes impossible to attain a sufficiently high adhesive strength if the ratio of the filler which does not contribute to the adhesion of the substrate and hydroxyapatite exceeds 20 wt%.
  • the ratio of the inorganic filler with respect to the organic polymer (in a dry state) be 1- 30. If said ratio is lower than 1, the surface of the inorganic filler is completely covered by the organic polymer, and the effects of depositing and fixing hydroxyapatite virtually vanish. If the ratio exceeds 40, on the other hand, it becomes impossible to hold the inorganic filler fixed to the substrate. In other words, the organic polymer no longer serves as a binder. As said organic polymer, it is necessary to select materials with high adhesive strengths vis-a-vis the substrate. If the substrate is an organic polymer, it is desirable that the same organic polymer be used as the organic polymer constituting the binder. There is no need to use a single material as said organic polymer, and accordingly, polymers obtained by blending, blocking, or grafting multiple types can also be employed.
  • the virtually saturated or supersaturated solution of hydroxyapatite refers to the aqueous solution disclosed in Japanese Patent Disclosure No. Tokkai Hei 2[1990]-25515.
  • the thickness of the hydroxyapatite film be 3-100 ⁇ m. If the thickness if less than 3 ⁇ , it may be consumed while it remains inside the body. If the thickness exceeds 100 ⁇ m, a significant strain is produced due to an expansion ratio difference between the substrate and hydroxyapatite in response to temperature and humidity variations. As a result, the hydroxyapatite layer is easily cracked, and said film is easily peeled via the resulting cracks. Moreover, the time required for forming the hydroxyapatite layer is prolonged, and accordingly, the production costs increase. Thus, there is no industrial significance in forming such a thick film.
  • the glass powder consisting principally of CaO and Si0 2 is a glass which contains CaO and Si0 2 (as oxides) within the following ranges: CaO: 20-60 mol%; Si0 2 : 40-80 mol% (CaO + Si0 2 : at least 70 mol%) . Moreover, at least 80% of the particles must be characterized by sizes of 100-600 ⁇ m.
  • the composition of a glass consisting principally of CaO and Si0 2 is disclosed in Japanese Patent Disclosure No. Tokkai Hei 2[1990]-25515.
  • the average dry film thickness of said organic polymer, which contains an inorganic filler and which exhibits an excellent adhesive strength with the substrate be 5-100 ⁇ m. If the thickness is less than 5 ⁇ , it becomes impossible to fix the inorganic filler to the substrate. If the thickness exceeds 100 ⁇ m, on the other hand, cohesive failures may be observed in the coating layer in actual use.
  • a glass consisting principally of CaO and SiO: employed in the present invention was prepared according to the following procedures.
  • Glass feed material mixing ratio 28.431 g of CaC0 2 , 2.289 g of MgO, 14.517 g of 0-Ca 2 P 2 O 7 , 0.249 g of CaF 2 , and 17.015 g of Si ⁇ 2 .
  • Glass composition 49.87 mol% of CaO, 35.46 mol% of Si0 2 , 7.153 mol% of P 2 0 5 , 7.111 mol% of MgO, and 0.399 mol% of CaF 2 .
  • a virtually saturated or supersaturated aqueous solution of hydroxyapatite was prepared according to the following composition.
  • the Ph at 36.5°C was adjusted at 7.4 by controlling the quantity of hydrochloric acid.
  • solution A 11.994 g of NaCl, 0.525 g of NaHC0 3 , 0.336 g of KCl, 0.342 g of K 3 HP0 4 -.3H 2 0, 0.458 g of MgCl 2 «6H 2 0, 0.417 g of CaCl 2 , 0.107 g of Na 2 S0 4 , approximately 68 m- of 1 N HCl, and 8.086 g of tris(hydroxymethyl)aminomethane.
  • FIG. 1 shows the shape of an implant component commonly referred to as a skin button
  • Figures 2 and 3 which are schematics of the process of hydroxyapatite coating on the surface of said implant component.
  • the notations signify the following: (11) : implant component consisting of a polyether-sulfone material (PES4100G, trademark of ICI Co.); (1) : upper adapter; (2) a lower adapter which is connected to the flange (3) of the upper adapter (1) and which connects the open holes (8) and (8a) via the open hole (8b) .
  • the notations signify the following: (4) and (4a) : containers; (5) : aforementioned inorganic filler; (6) : organic polymer solution; (7) : aqueous solution A.
  • the polyether-sulfone (PES4100G, manufactured by ICI Co.) implant component (11) shown in Figure l is partially dipped into the organic polymer solution (6) , which contains the inorganic filler (5) of the present invention and which exhibits an excellent adhesive strength with the substrate (11) [sic], and after it has been dried at room temperature over a 24-hour period, it was vacuum-dried at 60°C over a 5-hour period. After the vacuum-drying, said implant component (11) is immersed in the aqueous solution (A7) , as Figure 3 indicates.
  • PES4100G polyether-sulfone
  • the implant component After the implant component had been left in a 36.5°C thermostatic bath over a 1-week period, it is retrieved, and after it has been sufficiently washed with distilled water, it is dried at 60°C.
  • the bone-analogous hydroxyapatite film (11a) is formed on the surface of the implant component (11) which has been in contact with the organic polymer solution (6) in Figure 2 as a result of the foregoing procedures.
  • a total of 29 samples (23 for application examples and 6 for comparative examples) were prepared according to the aforementioned procedures, and two test pieces were allocated to each set of conditions. One was used in a fracture test, whereas the other was implanted into an adult dog in order to evaluate the biocompatibility. The following three categories, A through C, were evaluated.
  • the implant device shown in Figure 4 was prepared by using the other test piece of the aforementioned implant component (which was not used for the fracture test) . After said device had been sterilized by using gaseous ethylene oxide, it was implanted into the chest of an adult dog, as Figure 5 indicates. The conditions were observed after 1 day, 3 days, 1 week, 2 weeks, 3 weeks, and 1 month in order to evaluate the biocompatibility. In order to evaluate the biocompatibility in high sensitivity, the implant component was implanted in such a way that it will be partially exposed to the outside of the body and that the remainder will remain inside the body. After the device had been thus implanted, the conditions at the interface of the skin surface with the implant device was evaluated.
  • the upper tube (12) is connected to the open hole (8) of the implant component (11)
  • the lower tube (3) [sic], which is fixed by the fixation system (4) is connected to the open hole (8a) .
  • the Lure adapter (17) and the intermittent infusion plug (18) are attached to the front end of the upper tube (12) (and fixed by the fixing mechanism (19)).
  • the lower adapter (2) which contains the flange segment (3) of the implant component (11) , is buried beneath the skin surface (i.e., inside the body), as Figure 5 indicates.
  • the front end of the lower tube (13) is connected to the stationary catheter (16) via the connector (15) and extended toward a certain organ inside the body (not indicated in the figure) . (0034)
  • Barium sulfate was selected as an inorganic filler, and its particle size profile was controlled in such a way that 98 wt% (filler D) will be accounted for by particles with sizes of 3-100
  • a medical-grade polyurethane (SG65D, manufactured by Thermedics Co.) was employed as a substrate.
  • a medical- grade polyurethane identical to the substrate (SG65D, manufactured by Thermedics Co.) was employed as an organic polymer with an excellent [adhesive strength] with the substrate.
  • Cyclohexanone was employed as a solvent.
  • Application Examples 2 and 3 pertain to inorganic fillers A, B, C, and D shown in Table II, and it will be demonstrated that it is necessary that at least 80 wt% of the particles be within a particle size range of 3-100 ⁇ m.
  • Medical-grade polyurethane (SG65D, manufactured by Thermedics Co.) was employed as a substrate material.
  • Hydroxyapatite was coated according to procedures identical to those in Application Example 1 except that the organic polymer solution shown in Table IV was a solution into which the substrate was dipped. The evaluation results are shown in Table V.
  • implant components of the present invention can be obtained by using various inorganic fillers consisting of different materials shown in Table VI.
  • the coating film thickness was controlled by manipulating the organic polymer solution concentration and the dip frequency, and the five samples shown in Table VIII were obtained. Otherwise, procedures identical to those in Application Example 1 were carried out. Incidentally, the film thickness was 12 ⁇ m in Application Example 1. The evaluation results are shown in Table VIII.
  • implant component of the present invention has been explained with reference to several application examples above. It has long been known that the biocompatibility of hydroxyapatite is excellent. Due to low strengths, however, uses of sintered products as implant components have been limited to areas which are not exposed to high loads.
  • the present invention has successfully produced body implant components with bone-like coating of hydroxyapatite on the surface of organic polymer substrates by immersing the substrate in virtually saturated or supersaturated aqueous solution of hydroxyapatite.
  • the substrates had been prepared by dipping in an organic polymer solution, which contains inorganic filler powder with more than 80 wt% having grain diameters 3-100 ⁇ m, its dry weight ratio to the organic polymer 130 and good adhesive property with the substrate.
  • the body implant components thus obtained have excellent biocompatibility, 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)
  • Medicinal Chemistry (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Public Health (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

L'objectif de cette invention est d'obtenir un élément d'implant corporel bioactif, recouvert d'une couche d'hydroxyapatite, et qui présente une excellente compatibilité avec les tissus corporels, une résistance suffisamment élevée ainsi qu'une grande latitude de conception. L'élément se compose d'un substrat qui a été moulé de façon à présenter le profil d'un élément d'implant, et d'une couche d'hydroxyapatite appliquée par l'immersion du substrat dans une solution polymère organique qui contient une charge pulvérulente inorganique dont au moins 80 % en poids est composé de particules d'une grosseur comprise entre 3 et 100 νm, et dont le rapport pondéral avec le polymère organique (à l'état sec) est de 1-30. Le substrat est ensuite immergé dans une solution d'hydroxyapatite aqueuse présentant une concentration virtuellement saturée ou sursaturée.
PCT/US1992/008640 1991-10-15 1992-10-15 Element d'implant corporel bioactif, recouvert d'une couche d'apatite WO1993007916A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP3266019A JPH05103827A (ja) 1991-10-15 1991-10-15 生体活性アパタイト膜をコーテイングした生体インプラント部材
JP3/266019 1991-10-15

Publications (2)

Publication Number Publication Date
WO1993007916A2 true WO1993007916A2 (fr) 1993-04-29
WO1993007916A3 WO1993007916A3 (fr) 1993-05-27

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PCT/US1992/008640 WO1993007916A2 (fr) 1991-10-15 1992-10-15 Element d'implant corporel bioactif, recouvert d'une couche d'apatite

Country Status (3)

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JP (1) JPH05103827A (fr)
AU (1) AU2761292A (fr)
WO (1) WO1993007916A2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993023090A1 (fr) * 1992-05-20 1993-11-25 Sherwood Medical Company Vaisseau sanguin artificiel
WO1993023091A1 (fr) * 1992-05-20 1993-11-25 Sherwood Medical Company Trachee artificielle
EP0891783A1 (fr) * 1997-07-16 1999-01-20 Isotis B.V. Dispositif pour la régénération osseuse consistant d'un copolyester thermoplastique biodégradable et de cellules cultivées
US6228117B1 (en) 1997-07-16 2001-05-08 Isotis B.V. Device for tissue engineering bone

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101306803B1 (ko) * 2011-10-25 2013-09-10 오스템임플란트 주식회사 임플란트 표면의 생체활성을 증진시키는 유기용매를 이용한 임플란트 및 그 제조방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0264917A2 (fr) * 1986-10-20 1988-04-27 Shigeo Maruno Matériau composite biocompatible et son procédé de préparation
EP0389713A1 (fr) * 1989-03-29 1990-10-03 Kyoto University Procédé de revêtement avec une pellicule d'hydroxyapatite bioactive
WO1990011740A1 (fr) * 1989-04-08 1990-10-18 Robert Bosch Gmbh Disque intervertebral artificiel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0264917A2 (fr) * 1986-10-20 1988-04-27 Shigeo Maruno Matériau composite biocompatible et son procédé de préparation
EP0389713A1 (fr) * 1989-03-29 1990-10-03 Kyoto University Procédé de revêtement avec une pellicule d'hydroxyapatite bioactive
WO1990011740A1 (fr) * 1989-04-08 1990-10-18 Robert Bosch Gmbh Disque intervertebral artificiel

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPIL Week 9002, Derwent Publications Ltd., London, GB; AN 90-011580 *
DATABASE WPIL Week 9042, Derwent Publications Ltd., London, GB; AN 90-316446 *
JOURNAL OF MATERIALS SCIENCE. MATERIALS IN MEDICINE vol. 1, no. 4, November 1990, pages 233 - 238 Y. ABE ET AL. *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993023090A1 (fr) * 1992-05-20 1993-11-25 Sherwood Medical Company Vaisseau sanguin artificiel
WO1993023091A1 (fr) * 1992-05-20 1993-11-25 Sherwood Medical Company Trachee artificielle
EP0891783A1 (fr) * 1997-07-16 1999-01-20 Isotis B.V. Dispositif pour la régénération osseuse consistant d'un copolyester thermoplastique biodégradable et de cellules cultivées
US6228117B1 (en) 1997-07-16 2001-05-08 Isotis B.V. Device for tissue engineering bone

Also Published As

Publication number Publication date
JPH05103827A (ja) 1993-04-27
AU2761292A (en) 1993-05-21
WO1993007916A3 (fr) 1993-05-27

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