EP0797458A1 - Ciment osseux composite - Google Patents

Ciment osseux composite

Info

Publication number
EP0797458A1
EP0797458A1 EP95935505A EP95935505A EP0797458A1 EP 0797458 A1 EP0797458 A1 EP 0797458A1 EP 95935505 A EP95935505 A EP 95935505A EP 95935505 A EP95935505 A EP 95935505A EP 0797458 A1 EP0797458 A1 EP 0797458A1
Authority
EP
European Patent Office
Prior art keywords
cement
cement according
particles
polymer particles
mixture
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.)
Ceased
Application number
EP95935505A
Other languages
German (de)
English (en)
French (fr)
Inventor
Jacques Dejou
Wilhelm Joseph Pertot
Philippe Rolland
Jean-Pierre Proust
Marcel Camps
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.)
Euros SAS
Original Assignee
Euros SAS
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 Euros SAS filed Critical Euros SAS
Publication of EP0797458A1 publication Critical patent/EP0797458A1/fr
Ceased legal-status Critical Current

Links

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
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/0047—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L24/0073—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material with a macromolecular matrix
    • A61L24/0094—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material with a macromolecular matrix containing macromolecular fillers
    • 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
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001—Use of materials characterised by their function or physical properties
    • A61L24/0036—Porous materials, e.g. foams or sponges
    • 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
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001—Use of materials characterised by their function or physical properties
    • A61L24/0042—Materials resorbable by the body
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Definitions

  • the present invention relates to a new bone cement, useful as a composite filling material, hardenable by polymerization and gradually colonizable by bone.
  • the bone cements known in the prior art generally comprise a polymer powder and a crosslinking agent intended to ensure the hardening of the cement, (EP-A-0 430 705, EP-A-0 361 408), optionally added of a mineral filler (EP-A-0 225 706, WO-A- 82/01990).
  • These bone cements are generally prepared by mixing on the one hand a powder comprising the polymer and optionally the mineral filler, and on the other hand a liquid comprising monomers and polymerization initiators so as to react with the polymer powder, forming a resin which hardens on drying.
  • Such cements are described in particular in application FR-A-
  • the present invention therefore relates to a new bone cement consisting of:
  • a biocompatible organic pulverulent filler (b) comprising the mixture, on the one hand of porous polymer particles ensuring the penetration of fluids in the cement (bl), and on the other hand of biodegradable polymer particles intended to leave pores of large diameter in the cement obtained to have osteoconduction (b2);
  • the binding agent is used in the form of a liquid, mixed extemporaneously with a powder (pre-polymerized resinous powder particle) to form a paste.
  • the current The invention therefore also relates to a pulverulent mixture consisting of the mineral filler (a) and the organic filler (b) defined above, useful for preparing the cement according to the invention, by subsequently mixing it with an appropriate binding agent, in the form preformed powder or paste.
  • the biocompatible powdery mineral filler (a) consists of a material ensuring the mechanical strength of the cement and having good biocompatibility with regard to the medium in which the cement will be integrated.
  • the pulverulent mineral filler (a) generally consists of a silicate material, natural or synthetic, in particular by powder of glass, ceramic, baked clay, as well as by powder of aluminosilicates, such as for example kaolin or with a phosphocalcic compound.
  • the particles of mineral filler are substantially spherical and have an average diameter of less than 50 ⁇ m, advantageously between 5 and 20 ⁇ m, even more advantageously of approximately 10 ⁇ m.
  • diameter is meant according to the invention the dimensions of the meshes of a sieve in which the particles flow by gravity.
  • the particles of mineral filler will advantageously be silane, that is to say coated with a compatibilizing silane, for example methacryloxypropyl-trimethoxy-silane.
  • the biocompatible organic pulverulent filler (b) consists of a mixture of two types of polymer particles, on the one hand porous polymer particles (b1) and on the other hand of biodegradable polymer particles (b2).
  • the porous particles (bl) are intended to promote the penetration of fluids into the cement in order to promote the development of bone tissue, so that it gradually replaces the cement.
  • the particles (b1) are essentially in the form of porous balls or spheres, the average diameter of which is greater than or equal to 500 ⁇ m and the average porosity is between 30 and 70% (measured with a mercury porosimeter). They consist of a biocompatible polymeric material, that is to say having harmless properties with respect to the medium in which the cement will be used, also chemically compatible with the other constituents of the cement. The polymeric material will also be biodegradable, that is to say absorbable by the organism in which the cement is used, the rate of resorption being however slow enough to allow the maintenance of the cement and of its cohesion during the development of the bone tissue. by penetration of physiological fluids through the pores.
  • biocompatible biopolymers in particular crosslinked copolymers of glycol (meth) acrylate and of divinylbenzene.
  • copolymers are advantageously obtained by emulsion copolymerization, a two-phase aqueous suspension consisting on the one hand of a mixture of glycol (meth) acrylate, of divinylbenzene and of toluene in respective weight proportions of between 8/1 / 10 and 4 / 1/6, preferably 6/1/8.
  • the initiation of the copolymerization is carried out by a radical polymerization initiator soluble in the above organic phase but insoluble in water.
  • the initiator is used in proportions of between 0J and 1% by weight.
  • the second phase the aqueous biphasic phase also contains gum arabic, in particular acacia gum arabic (titrating from 0.5 to 1.5%) and a surfactant such as metal lauryl sulfate alkaline, especially sodium.
  • gum arabic in particular acacia gum arabic (titrating from 0.5 to 1.5%)
  • surfactant such as metal lauryl sulfate alkaline, especially sodium.
  • the organic phase is divided into droplets which solidify by polymerization giving the macroporous beads.
  • the biodegradable polymer particles (b2) are made up of a rapidly biodegradable polymeric material to give way to pores in the cement, unlike the material constituting the porous particles (b1) whose resorption must be slow and controlled.
  • They are also essentially in the form of balls, or spheres, the average diameter of which is between 150 and 400 ⁇ m, so as to leave in the cement pores of the same diameter creating osteoconduction.
  • the particles (b2) consist of usual biodegradable hydrophilic (co) polymers, in particular (co) polymers comprising units derived from (meth) acrylic acid and / or lactic acid and / or glycolic acid, or polyacryloid acid.
  • R2 represents a hydroxy carbonyl group, a lower C 1 -C 4 alkoxy carbonyl group, for example ethoxy carbonyl, or a hydroxy group
  • R3 represents a hydrogen atom or a hydroxy group, or alternatively
  • the biodegradable polymer is a copolymer of lactic acid and glycolic acid comprising monomers L and D of lactic acid, in particular copolymers obtained by the polymerization of L-lactide , glycolid ci of D-lactide in a weight ratio close to 3: 4: 3, respectively.
  • the binding agent (c) consists of a resin p ⁇ >l> ⁇ e. formed extemporaneously by mixing monomers and / or p. MIR ⁇ of low molecular weight and a polymerization initiator.
  • This polymer resin must, of course, be chemically combined with the other constituents of the cement according to Riin Cmi ⁇ n. lk- must also have the characteristics of biocompatibility common to all of these constituents, taking into account their medical use.
  • the polymer resin of the binding agent (c) is a bis-GMA resin.
  • the polymer resin is obtained by polymerization of ethylene glycol dimethacrylate.
  • the cement according to the invention is prepared by mixing and kneading the pulverulent mixture (a and b) according to the invention with a solution or a paste comprising the binding agent (c), in suitable proportions.
  • the cement is obtained by mixing the pulverulent mixture with a powder consisting of monomers and / or polymers of low molecular weight, precursors of the polymer resin, then adding to the mixture obtained an aqueous solution comprising a polymerization initiator, such as benzoyl peroxide, and if necessary an agent delaying the polymerization.
  • a polymerization initiator such as benzoyl peroxide
  • the powdery mineral filler (a) represents between 60 and 80% by weight of the powdery mixture (a and b), preferably about 70% by weight.
  • the weight ratio (b1) / (b2) between the two constituents of the pulverulent organic charge (b) is advantageously between 0.20 and 0.35.
  • the weight ratio between the constituents of the pulverulent mixture (a and b) and the binding agent (c) is advantageously between 4 and 5.5.
  • phase B 18% water.
  • the GMA + divinylbenzene + toluene mixture with the reaction initiator (benzoyl peroxide) is carried out at the last moment, to avoid immediate polymerization.
  • the mixture of phases A + B and the emulsion C are added to 200 ml of deionized water.
  • the lauryl sulfate and gum arabic are removed by washing with ordinary water.
  • the polymer which has been chosen is a copolymer of lactic acid and glycolic acid (PLa 30 Ga 40).
  • the powder mixture consists of the following materials, per 100 g of powder:
  • silane mineral fillers based on quartz, barium glass and silica, with a particle size of approximately 10 ⁇ m;
  • biodegradable polymer beads (b2) obtained according to the protocol described in Example 2. The constituents are mixed by kneading.
  • EXAMPLE 4 Preparation of a bone cement 100 g of the pulverulent mixture obtained above are added to 21.06 g of a pulverulent bis-GMA resinous organic matrix.
  • an aqueous solution comprising a polymerization initiator, in particular benzoyl peroxide and an appropriate retarding agent so as to regulate the setting time of the cement according to the invention.
  • a polymerization initiator in particular benzoyl peroxide
  • an appropriate retarding agent so as to regulate the setting time of the cement according to the invention.
  • the cement obtained may further comprise an appropriate dye.
  • the physico-mechanical properties of the final product will be at least equal to those given by the ISO 5833 standard relating to bone cements based on PMMA.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Epidemiology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Surgery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dispersion Chemistry (AREA)
  • Composite Materials (AREA)
  • Materials For Medical Uses (AREA)
EP95935505A 1994-10-17 1995-10-17 Ciment osseux composite Ceased EP0797458A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9412369A FR2725625A1 (fr) 1994-10-17 1994-10-17 Ciment osseux composite
FR9412369 1994-10-17
PCT/FR1995/001364 WO1996011714A1 (fr) 1994-10-17 1995-10-17 Ciment osseux composite

Publications (1)

Publication Number Publication Date
EP0797458A1 true EP0797458A1 (fr) 1997-10-01

Family

ID=9467927

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95935505A Ceased EP0797458A1 (fr) 1994-10-17 1995-10-17 Ciment osseux composite

Country Status (3)

Country Link
EP (1) EP0797458A1 (enrdf_load_stackoverflow)
FR (1) FR2725625A1 (enrdf_load_stackoverflow)
WO (1) WO1996011714A1 (enrdf_load_stackoverflow)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1058689C (zh) * 1998-02-05 2000-11-22 华东理工大学 含有成孔剂的多孔磷酸钙骨水泥及其应用
US6689823B1 (en) 1999-03-31 2004-02-10 The Brigham And Women's Hospital, Inc. Nanocomposite surgical materials and method of producing them
GB0514076D0 (en) * 2005-07-08 2005-08-17 Depuy Int Ltd Bioactive bone cement composition
US10729600B2 (en) 2015-06-30 2020-08-04 The Procter & Gamble Company Absorbent structure
US11020289B2 (en) 2015-11-04 2021-06-01 The Procter & Gamble Company Absorbent structure
EP3370673B1 (en) 2015-11-04 2022-03-30 The Procter & Gamble Company Absorbent structure
HUE066955T2 (hu) 2015-11-04 2024-09-28 Procter & Gamble Nedvszívó struktúra
EP3370664B1 (en) 2015-11-04 2022-01-26 The Procter & Gamble Company Absorbent article comprising an absorbent structure
WO2019090293A1 (en) 2017-11-06 2019-05-09 The Procter & Gamble Company Absorbent article with conforming features

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2670114B1 (fr) * 1990-12-10 1993-01-22 Science Medecine Materiau biocompatible et partiellement biodegradable, tel qu'un ciment pour scellement de prothese notamment orthopedique.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9611714A1 *

Also Published As

Publication number Publication date
WO1996011714A1 (fr) 1996-04-25
FR2725625A1 (fr) 1996-04-19
FR2725625B1 (enrdf_load_stackoverflow) 1997-02-21

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