Method for the manufacture of intraluminal stents of bioresorbable polymeric material

• US 5,935,506 A
• Filed: 10/17/1996
• Issued: 08/10/1999
• Est. Priority Date: 10/24/1995
• Status: Expired due to Fees

• Current Assignee: Biotronik Mess-Und Therapiegeraete GmbH & Company Ingenieurbuero Berlin (Biotronik SE & Company KG)
• Original Assignee: Biotronik Mess-Und Therapiegeraete GmbH & Company Ingenieurbuero Berlin (Biotronik SE & Company KG)
• Inventors: Schmitz, Klaus-Peter, Behrend, Detlef
• Primary Examiner(s): Timm, Catherine
• Assistant Examiner(s): MCDOWELL, SUZANNE E
• Application Number:
  US08/733,172
• Time in Patent Office: 1,027 Days
• Field of Search: 264/255, 264/305, 264/306, 264/310, 264/313, 264/317, 264/221, 264/338, 264/400, 623/900, 623/901, 604/265
• US Class Current: 264/400
• CPC Class Codes: A61F 2/82 Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents stent-grafts for tubular structures of the body other than blood vessels A61F2/04; stent-grafts for blood vessels A61F2/07; instruments specially adapted for placement or removal of stents or stent-grafts A61F2/95; for closing wounds, or holding wounds closed A61B17/04 - A61B17/115; dilators A61M29/00
• CPC Class Codes: A61L 31/06 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds A61L31/041 takes precedence
• CPC Class Codes: A61L 31/148 Materials at least partially resorbable by the body
• CPC Class Codes: B23K 2103/42 Plastics B23K2103/16 takes precedence
• CPC Class Codes: B23K 2103/50 Inorganic material, e.g. metals, not provided for in B23K2103/02 – B23K2103/26
• CPC Class Codes: B29C 41/08 Coating a former, core or other substrate by spraying or fluidisation, e.g. spraying powder spray-up of reinforcing fibres B29C70/305
• CPC Class Codes: B29C 41/14 Dipping a core B29C41/10 takes precedence
• CPC Class Codes: B29C 41/22 Making multilayered or multicoloured articles
• CPC Class Codes: C08L 67/04 Polyesters derived from hydroxycarboxylic acids, e.g. lactones C08L67/06 takes precedence
• CPC Class Codes: Y10S 623/90 Stent for heart valve
• CPC Class Codes: Y10S 623/901 Method of manufacturing prosthetic device

Abstract

A method for the manufacture of intravascular stents of bioresorbable material comprises the following steps:

preparing a viscous solution of poly-β-hydroxybutanoic acid as a bioresorbable polymeric material in a solvent,

successively coating a male mold core with layers of the polymer solution in several steps by precipitation of the polymeric material by the solvent being evaporated and by the layer previously precipitated being dissolved at least partially for a homogeneous stent blank to build up,

drawing the stent blank off the male mold core, and

subsequently treating the stent blank to finish the shaping of the stent.

Claims

1. A method for the manufacture of intravascular stents of bioresorbable polymeric material, comprising the following steps:

preparing a viscous polymer solution of poly-β

-hydroxybutanoic acid as a bioresorbable polymeric material in a solvent,

successively coating a surface of a male mold core (2) with layers of the polymer solution in several steps by precipitation of the polymeric material by the solvent being evaporated and by the layer previously precipitated being dissolved at least partially for a homogeneous stent blank (1) to build up,

drawing the stent blank (1) off the male mold core (2), and

subsequently treating the stent blank (1) to finish the shaping of the stent.

2. A method according to claim 1, wherein for successively coating the male mold core (2) with layers of the polymer solution, the male mold core (2) is alternatively dipped for several times into the polymer solution and removed from the latter for the solvent to evaporate from the layer (9, 11, 12, 13) of polymer solution depositing.

3. A method according to claim 1, wherein for successively coating the male mold core (2) with layers of the polymer solution, the latter is poured over the male mold core (2) in several successive operations, the previously adhering layer (9, 11, 12, 13) of polymer solution, between each pouring operation, being at least partially dissolved by the subsequent layer (11, 12, 13) of polymer solution and the polymeric material being precipitated by evaporation of the solvent.

4. A method according to claim 1, wherein the male mold core (2) is rotated during the build-up of the stent blank (1).

5. A method according to claim 1, wherein preparing the polymer solution consists in dissolving in chloroform poly-β

-hydroxybutanoic acid as a powder in a percentage of 2 to 3% by weight referred to the total quantity of solution.

6. A method according to claim 5, wherein dissolving takes place by stirring at temperatures ranging between 50 and 70°

C.

7. A method according to claim 1, wherein for adjustment of the mechanical properties of the stent, a biocompatible plasticizer of a concentration of 5 to 50% by weight is added to the polymer solution.

10. A method according to claim 1, wherein at least one of a pharmaceutical anticoagulant and a cell-proliferation-inhibiting agent (10) is added to the polymer solution.

14. A method according to claim 1, wherein prior to the coating of the male mold core (2) with the polymer solution, the latter is filtered through a frit.

15. A method according to claim 1, wherein the stent blank (1) is subsequently treated by at least one of laser-beam cutting and water-jet cutting.

16. A method according to claim 7, wherein said biocompatible plasticizer is ethyl citrate.

19. A method according to claim 1, wherein said successively coating comprises applying a first coating of said polymer solution containing a biocompatible plasticizer and a pharmaceutical anticoagulant to form a first layer;

after evaporation of solvent from said first layer, applying thereto a second solution of said polymer containing a biocompatible plasticizer to form a second layer integral with said first layer;

after evaporation of solvent from said second layer, applying a third layer of said polymer solution containing a biocompatible plasticizer, said third layer optionally also containing particles of an x-ray contrast medium, thereby providing a third layer integral with said second layer; and

, after evaporating solvent from said third layer, optionally applying a fourth layer of said polymer solution optionally containing particles of an x-ray contrast medium therein.

20. A method according to claim 19, comprising only three or four of said applications of coatings.

8. A method for the manufacture of intravascular stents of bioresorbable polymeric material, comprising:

preparing a viscous chloroform solution of poly-β

-hydroxy-butanoic acid as a bioresorbable polymeric material,

applying the chloroform solution of poly-β

-hydroxy-butanoic acid directly to a surface of the male mold core (2), and successively coating with additional layers of the solution by precipitation of the polymeric material by evaporation of the chloroform and by the layer previously precipitated being dissolved at least partially for a homogeneous stent blank (1) to build up on said male mold surface,

removing the stent blank (1) from the male mold core (2), and subsequently

finishing the shaping of the stent;

wherein prior to being coated with the solution, the male mold core (2) is coated with a biocompatible release agent (8), which is insoluble in chloroform, but soluble in other solvents.

9. A method according to claim 8, wherein the release agent used is a concentrated sugar solution, which is dissolved by distilled water before the stent blank (1) is drawn off the male mold core (2).

17. A method according to claim 9, wherein ethyl citrate of a concentration of 5-50% by weight is added to the solution.

18. A method according to claim 8, wherein the release agent used is a concentrated glucosid solution.

11. A method for the manufacture of intravascular stents of bioresorbable polymeric material, comprising:

preparing a viscous solution of poly-β

-hydroxy-butanoic acid as a bioresorbable polymeric material in a solvent,

successively coating a male mold core (2) with layers of the polymeric material in several steps by precipitation of the polymeric material by evaporation of the solvent and by the layer previously precipitated being dissolved at least partially for a homogeneous stent blank (1) to build up,

removing the stent blank (1) from the male mold core (2), and subsequently

finishing the shaping of the stent;

wherein at least one of a pharmaceutical anticoagulant and a cell-proliferation-inhibiting agent (10) is added to the solution, and is incorporated in the volume of the stent homogeneously for continuous release during bioresorption of the stent.

12. A method for the manufacture of intravascular stents of bioresorbable polymeric material, comprising:

preparing a viscous solution of poly-β

-hydroxy-butanoic acid as a bioresorbable polymeric material in a solvent,

successively coating a male mold core (2) with layers of the polymeric material in several steps by precipitation of the polymeric material by the evaporation of solvent and by the layer previously precipitated being dissolved at least partially for a homogeneous stent blank (1) to build up,

removing the stent blank (1) from the male mold core (2), and subsequently

finishing the shaping of the stent;

wherein at least one of a pharmaceutical anticoagulant and a cell-proliferation-inhibiting agent (10) is added to the solution, and is spread in one or several layers (9) for continuous release during bioresorption of the stent.

13. A method for the manufacture of intravascular stents of bioresorbable polymeric material, comprising:

preparing a viscous solution of poly-β

-hydroxy-butanoic acid as a bioresorbable polymeric material in a solvent,

successively coating a male mold core (2) with layers of the polymeric material in several steps by precipitation of the polymeric material by the evaporation of solvent and by the layer previously precipitated being dissolved at least partially for a homogeneous stent blank (1) to build up, and wherein particles (14) of at least one of silver and silver alloys are added to the solution for being incorporated as an X-ray contrast medium and inflammation-inhibiting agent into the volume of the stent,

removing the stent blank (1) from the male mold core (2), and subsequently

finishing the shaping of the stent.