Lubricious antithrombogenic catheters, guidewires and coatings

• US 5,135,516 A
• Filed: 12/15/1989
• Issued: 08/04/1992
• Est. Priority Date: 12/15/1989
• Status: Expired due to Term

• Current Assignee: Boston Scientific Scimed (Boston Scientific Corporation)
• Original Assignee: Boston Scientific Corporation
• Inventors: Sahatjian, Ronald, Amplatz, Kurt
• Primary Examiner(s): MILLIN, VINCENT A
• Application Number:
  US07/451,507
• Time in Patent Office: 963 Days
• Field of Search: 604/266, 604/265, 427/2, 427/230, 427/412.1
• US Class Current: 604/265
• CPC Class Codes: A61L 33/0023 using a quaternized group or a protonated amine group of the substrate
• CPC Class Codes: A61L 33/0029 using an intermediate layer of polymer
• CPC Class Codes: A61M 2025/0046 Coatings for improving slidability
• CPC Class Codes: A61M 2025/0056 provided with an antibacterial agent, e.g. by coating, residing in the polymer matrix or releasing an agent out of a reservoir
• CPC Class Codes: A61M 25/0045 multi-layered, e.g. coated coating materials A61L29/08
• CPC Class Codes: C08L 33/00 Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 33/02 Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• CPC Class Codes: C08L 35/00 Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers

Abstract

Method for rendering a preformed article lubricious and antithrombogenic and a device being the same. On the surface of the article a thin coating of a biologically compatible, lubricious, hydrophilic polymer including acid groups, is provided. On the coating, ammonium cation, and heparin are applied in the manner that heparin is bound by electrostatic attraction to the ammonium cation of the coating to permit time release of heparin. A buffer solution may be applied in a manner to act to enhance the lubriciousness of the coating.

Claims

1. Method for rendering a surface of a preformed article lubricious and antithrombogenic comprising:

providing on said surface a thin coating of biologically compatible, lubricious, hydrophilic polymer including acid groups, and thereafter applying to said coating ammonium cation, heparin and buffer solution in the manner that heparin is bound by electrostatic attraction to ammonium cation of said coating to permit time release of heparin in the presence of body fluid, and said buffer solution acts to enhance lubriciousness of said coating.

3. The method of claims 1 or 2 further comprising:

applying to said lubricious polymer coating ammonium cation and heparin, and, thereafter applying buffer solution.

4. The method of claim 3 wherein ammonium cation is applied before heparin is applied.

5. The method of claims 1 or 2 further comprising:

applying to said lubricious polymer coating ammonium cation, applying buffer solution and thereafter, applying heparin.

6. The method of claims 1 or 2 further comprising applying to said lubricious polymer coating, buffer solution and thereafter applying ammonium cation and heparin.

7. The method of claims 1 or 2 wherein ammonium cation is provided by applying an aqueous solution.

8. The method of claims 1 or 2 further including drying said polymer coating after applying ammonium cation.

9. The method of claims 1 or 2 further including drying said coating before providing buffer solution.

10. The method of claims 1 or 2 wherein buffer solution of sodium bicarbonate buffer is applied to said coating to enhance lubriciousness.

11. The method of claims 1 or 2 comprising applying buffer solution to enhance lubriciousness by formation of salts of said acid groups.

12. The method of claims 1 or 2 comprising reducing the coefficient of friction of said coating by applying a buffer solution wherein after applying said buffer solution said coefficient of friction is less than about 0.1.

13. The method of claims 1 or 2 wherein said providing lubricious polymer includes:

providing to said surface a primer solution including isocyanate and providing a hydrophilic polymer coating to said isocyanate.

14. The method of claims 1 or 2 wherein said hydrophilic polymer has a molecular weight from about 200,000 to 5,000,000 and is selected from the group consisting of polyacrylic acid, crotonic acid, maleic acid and amino acids and their derivatives and coploymers.

15. The method of claims 1 or 2 wherein said preformed surface is selected from the group consisting of nylon, polyurethane, polyester, "C-Flex", "Percuflex", "Kraton", and polyethylene.

16. The method of claims 1 or 2 wherein said ammonium cation is benzalkonium cation formed by dissociation of benzalkonium chloride.

17. The method of claims 1 or 2 wherein said ammonium cation is provided in a manner causing reaction of said cation with acid groups to form ammonium salts.

18. The method of claims 1 or 2 wherein said polymer and heparin are applied in the manner to provide a coating which is about 1.0 to 10 microns thick, when dry.

19. The method of claim 18 wherein said coating is about 2 to 5 microns when dry.

20. The method of claims 1 or 2 wherein the thickness of said coating increases by about six to ten times when wet.

21. The method of claims 1 or 2 wherein the thickness of said coating is about 20 microns when wet.

22. The method of claims 1 or 2 wherein said coating is applied to an angioplastic catheter.

23. The method of claims 1 or 2 wherein said coating is applied to angioplasty balloon catheter.

24. The method of claims 1 or 2 wherein said coating is applied to a guidewire.

25. The method of claim 24 wherein said guidewire is a polymer coated guidewire.

47. The invention of any one of claims 1, 2, 26, 27, 45 or 46 wherein said polymer is polyacrylic acid.

48. The invention of claim 47 wherein said surface is a metal surface.

2. Method for rendering a surface of a preformed article lubricious and antithrombogenic comprising:

providing on said surface a thin coating of biologically compatible, lubricious, hydrophilic polymer including acid groups, and thereafter applying to said coating ammonium cation and heparin in the manner that heparin is bound, by electrostatic attraction to ammonium cation of said coating to permit time release of heparin in the presence of body fluid, the thickness of said lubricious and antithrombogenic coating being of the order of about 10 microns or less when dry.

26. A medical device for use within the body formed of a dimensionally stable base material forming the main body of said device and having a thin lubricious coating on its surface, said coating being capable of reducing the thrombogenicity of said surface and comprising:

a lubricious, hydrophilic, swellable polymer, being on said surface said polymer having covalently bonded acid groups, and incorporating noncovalently bonded ammonium cations, and heparin bound in a manner permitting time release in the presence of body fluid, the thickness of said lubricious and antithrombogenic coating being of the order of 10 microns or less when dry.

28. The device of claims 26 or 27 wherein said polymer contains ammonium salts.

29. The device of claims 26 or 27 wherein said polymer contains acid salts having cations other than said ammonium cation.

30. The device of claims 26 or 27 wherein polymer includes sodium salts of said acid.

31. The device of claims 26 or 27 comprising a lubricious, antithrombogenic catheter device capable of substantially maintaining its internal and external diameter when in contact with blood for extended periods said catheter being formed of a nonswellable, dimensionally stable material.

32. The device of claim 29 wherein said catheter is an angioplastic catheter having an outer diameter of no more than 12 French.

33. The device of claim 29 wherein said catheter is adapted for operation in the coronary vascular system.

34. The device of claims 26 or 27 wherein said surface is a dimensionally stable polymer selected from the group consisting of nylon, "C-Flex", "Percuflex", "Kraton", polyurethane, polyester and polyethylene.

35. The device of claims 26 or 27 comprising an angioplasty balloon catheter wherein at least the balloon of said catheter is coated.

36. The device of claims 26 or 27 comprising a guide wire.

37. The device of claim 36 wherein said guidewire is a polymer coated guidewire.

38. The device of claims 26 or 27 having a surface of coefficient of friction of 0.1 or less

39. The device of claims 26 or 27 wherein said coating is about 1.0 to 10 microns thick when dry.

40. The device of claim 37 wherein said coating is 2 to 5 microns thick when dry.

41. The device of claims 26 or 27 wherein said coating increases in thickness by about a factor of six to ten when wet.

42. The device of claims 26 or 27 wherein said coating is about 20 microns when wet.

43. The device of claims 26 or 27 wherein said coating includes a polymer with a molecular weight from about 200,000 to 5,000,000 selected from the group consisting of polyacrylic acid, crotonic acid, maleic acid and amino acids and their derivatives and copolymers.

44. The method of claims 26 or 27 wherein said ammonium cation is the benzalkonium cation formed by dissociation of benzalkonium chloride.

27. A medical device for use within the body formed of a dimensionally stable base material forming the main body of said device and having a thin lubricious coating on its surface, said coating being capable of reducing the thrombogenicity of said surface and comprising:

a lubricious, hydrophilic, swellable polymer being on said surface, said polymer having covalently bonded acid groups and incorporating noncovalently bonded ammonium cations, and heparin bound in a manner permitting time release in the presence of body fluid, and acid salts to enhance lubricity.

45. A medical device for use within the body formed of a dimensionally stable base material forming the main body of said device and having a thin lubricious coating on its surface, said coating being capable of reducing the thrombogenicity of said surface and formed by the process comprising:

providing on said surface a thin coating of biologically compatible, lubricious, hydrophilic polymer including acid groups, and thereafter applying to said coating ammonium cation, heparin and buffer solution in the manner that heparin is bound by electrostatic attraction to ammonium cation of said coating to permit time release of heparin in the presence of body fluid, and said buffer solution acts to enhance lubriciousness of said coating.

46. A medical device for use within the body formed of a dimensionally stable base material forming the main body of said device and having a thin lubricious coating on its surface, said coating being capable of reducing the thrombogenicity of said surface and formed by the process comprising:

providing on said surface a thin coating of biologically compatible, lubricious, hydrophilic polymer including acid groups, and thereafter applying to said coating ammonium cation and heparin in the manner that heparin is bound, by electrostatic attraction to the ammonium cation of said coating to permit time release of heparin in the presence of body fluid, the thickness of said lubricious and antithrombogenic coating being of the order of about 10 microns or less when dry.