Multilayered polymer structure for medical products

• US 6,083,587 A
• Filed: 09/22/1997
• Issued: 07/04/2000
• Est. Priority Date: 09/22/1997
• Status: Expired due to Term

• Current Assignee: Baxter International Inc.
• Original Assignee: Baxter International Inc.
• Inventors: Smith, Sidney T., Rosenbaum, Larry, Nebgen, Gregg, Giovanetto, Steven, Buchanan, Bradley, Fan, Suchuan C., Ding, Y. Samuel
• Primary Examiner(s): KILIMAN, LESZEK B
• Application Number:
  US08/934,924
• Time in Patent Office: 1,016 Days
• Field of Search: 428/36.6, 428/36.7, 428/343, 428/332, 428/474.4, 428/476.3, 428/500, 428/515, 428/518
• US Class Current: 428/36.6
• CPC Class Codes: B29C 48/08 flexible, e.g. films
• CPC Class Codes: B29C 48/09 Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
• CPC Class Codes: B29C 48/185 comprising six or more components, i.e. each component being counted once for each time it is present, e.g. in a layer
• CPC Class Codes: B32B 2323/046 LDPE, i.e. low density polyethylene
• CPC Class Codes: B32B 2377/00 Polyamides
• CPC Class Codes: B32B 2535/00 Medical equipment, e.g. bandage, prostheses, catheter medical patches B32B2556/00
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/32 comprising polyolefins comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30
• CPC Class Codes: B32B 27/34 comprising polyamides
• CPC Class Codes: B32B 37/153 at least one layer is extruded and immediately laminated while in semi-molten state
• CPC Class Codes: Y10T 428/1379 Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
• CPC Class Codes: Y10T 428/1383 Vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit is sandwiched between layers [continuous layer]
• CPC Class Codes: Y10T 428/26 Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
• CPC Class Codes: Y10T 428/28 Web or sheet containing structurally defined element or component and having an adhesive outermost layer
• CPC Class Codes: Y10T 428/31725 Of polyamide
• CPC Class Codes: Y10T 428/3175 Next to addition polymer from unsaturated monomer[s]
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31909 Next to second addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/3192 Next to vinyl or vinylidene chloride polymer

Abstract

The present invention provides a multiple layer structure for fabricating medical products. The layer structure has a core layer of an ethylene vinyl alcohol copolymer having an ethylene content of about 25-45 mole percent, a solution contact layer of a polyolefin positioned on a first side of the core layer, an outer layer positioned on a second side of the core layer opposite the solution contact layer, the outer layer being selected from the group consisting of polyamides, polyesters and polyolefins; two tie layers--one of each adhered to the first and second sides of the core layer and positioned between the solution contact layer and the core layer and between the outer layer and the core layer, and wherein the structure is produced in a cast coextrusion process.

Claims

1. A multiple layer structure for fabricating medical products comprising:

a core layer of an ethylene vinyl alcohol copolymer having an ethylene content of about 25-45 mole percent;

a solution contact layer of a polyolefin positioned on a first side of the core layer;

an outer layer positioned on a second side of the core layer opposite the solution contact layer, the outer layer being selected from the group consisting of polyamides and polyesters;

two tie layers, one of each adhered to the first and second sides of the core layer and positioned between the solution contact layer and the core layer and between the outer layer and the core layer;

and wherein the structure is produced in a cast extrusion process essentially free of water soluble slip agents.

2. The structure of claim 1 wherein the polyamide is selected from aliphatic polyamides resulting from the condensation reaction of di-amines having a carbon number within a range of 2-13, aliphatic polyamides resulting from a condensation reaction of di-acids having a carbon number within a range of 2-13, polyamides resulting from the condensation reaction of dimer fatty acids, and amide containing copolymers.

3. The structure of claim 1 wherein the polyamide is selected from the group of polyamides produced in a ring-opening reaction of lactams having from 4-12 carbons.

4. The structure of claim 3 wherein the polyamide is nylon 12.

5. The structure of claim 1 wherein the polyolefin of the solution contact layer is selected from the group consisting of homopolymers and copolymers of alpha-olefins containing from 2 to about 20 carbon atoms.

6. The structure of claim 5 wherein the polyolefin of the solution contact layer is a homopolymer or a copolymer of an alpha-olefin having from 2 to about 10 carbons.

7. The structure of claim 6 wherein the polyolefin is selected from the group consisting of ethylene copolymers, and butene-1 copolymers.

8. The structure of claim 7 wherein the ethylene copolymer of the solution contact layer is an ethylene-butene-1 copolymer.

9. The structure of claim 8 wherein the ethylene copolymer of the solution contact layer is produced using a metallocene catalyst.

10. The structure of claim 1 wherein the tie layer is a polyolefin polymer or copolymer blended with a polyethylene copolymer grafted with a carboxylic acid anhydride or a carboxylic acid.

11. The structure of claim 10 wherein the carboxylic acid anhydride is an unsaturated fused ring carboxylic acid anhydride.

12. The structure of claim 11 wherein the carboxylic acid anhydride is a maleic anhydride.

13. The structure of claim 1 wherein the low molecular weight water soluble fraction of the structure is less than 1.0 ppt as measured for a container having a surface area of 450 cm² and containing 250 ml of saline solution.

14. The structure of claim 1 wherein the low molecular weight water soluble fraction of the structure is less than 100 ppm as measured for a container having a surface area of 450 cm² and containing 250 ml of saline solution.

15. The structure of claim 1 wherein the low molecular weight water soluble fraction of the structure is less than 10 ppm as measured for a container having a surface area of 450 cm² and containing 250 ml of saline solution.

16. The structure of claim 1 wherein the solution contact layer is from about 3-8 mils thick, the core layer is from about 0.2-2.5 mils thick, the outer layer is from about 0.2-2.0 mils thick, and the tie layers are from 0.2-1.2 mils thick to define an asymmetrical structure about the core layer.

17. A multiple layer structure for fabricating medical products comprising:

a core layer of an ethylene vinyl alcohol copolymer having an ethylene content of about 25-45 mole percent, and having a thickness of about 0.2-2.5 mils;

a solution contact layer of an ethylene and α

-olefin copolymer positioned on a first side of the core layer, the solution contact layer having a thickness of about 3-8 mils;

an outer layer positioned on a second side of the core layer opposite the solution contact layer, the outer layer being a polyamide having a thickness from 0.2-2.0 mils;

two tie layers, one of each adhered to the first and second sides of the core layer and positioned between the solution contact layer and the core layer and between the outer layer and the core layer; and

wherein the structure is produced in a cast coextrusion process essentially free of water soluble slip agents.

18. The structure of claim 17 wherein the polyamide is selected from aliphatic polyamides resulting from the condensation reaction of di-amines having a carbon number within a range of 2-13, aliphatic polyamides resulting from a condensation reaction of di-acids having a carbon number within a range of 2-13, polyamides resulting from the condensation reaction of dimer fatty acids, and amide containing copolymers.

19. The structure of claim 17 wherein the polyamide is selected from the group of polyamides produced in a ring-opening reaction of lactams having from 4-12 carbons.

20. The structure of claim 19 wherein the polyamide is nylon 12.

21. The structure of claim 17 wherein the alpha-olefin of the solution contact layer contain from 2 to about 20 carbon atoms.

22. The structure of claim 17 wherein the alpha-olefin of the solution contact layer contain from 2 to about 10 carbons.

23. The structure of claim 22 wherein the alpha-olefin is a butene-1.

24. The structure of claim 17 wherein the ethylene and alpha-olefin copolymer of the solution contact layer is produced using a metallocene catalyst.

25. The structure of claim 17 wherein the tie layer is a polyolefin polymer or copolymer blended with a polyethylene copolymer grafted with a carboxylic acid anhydride or a carboxylic acid.

26. The structure of claim 25 wherein the carboxylic acid anhydride is an unsaturated fused ring carboxylic acid anhydride.

27. The structure of claim 26 wherein the carboxylic acid anhydride is a maleic anhydride.

28. The structure of claim 17 wherein the low molecular weight water soluble fraction of the structure is less than 1.0 ppt as measured for a container having a surface area of 450 cm² and containing 250 ml of saline solution.

29. The structure of claim 17 wherein the low molecular weight water soluble fraction of the structure is less than 100 ppm as measured for a container having a surface area of 450 cm² and containing 250 ml of saline solution.

30. The structure of claim 17 wherein the low molecular weight water soluble fraction of the structure is less than 10 ppm as measured for a container having a surface area of 450 cm² and containing 250 ml of saline solution.

31. A method for fabricating a multilayered structure comprising the steps of:

providing a core layer of an ethylene vinyl alcohol copolymer having an ethylene content of about 25-45 mole percent;

providing a solution contact layer of a polyolefin positioned on a first side of the core layer;

providing an outer layer positioned on a second side of the core layer opposite the solution contact layer, the outer layer being selected from the group consisting of polyamides, and polyesters;

cast coextruding the outer layer, the core layer and the solution contact layer to define a multilayered structure; and

wherein the step of cast coextruding is carried essentially free of water soluble slip agents.

32. The method of claim 31 wherein the step of cast coextruding the multilayered structure further includes the steps of providing a first tie layer and a second tie layer, and positioning the first tie layer between the outer layer and the core layer, and positioning the second tie layer between the inner layer and the core layer.

33. The method of claim 31 wherein the polyamide is selected from aliphatic polyamides resulting from the condensation reaction of di-amines having a carbon number within a range of 2-13, aliphatic polyamides resulting from a condensation reaction of di-acids having a carbon number within a range of 2-13, polyamides resulting from the condensation reaction of dimer fatty acids, and amide containing copolymers.

34. The method of claim 31 wherein the polyamide is selected from the group of polyamides produced in a ring-opening reaction of lactams having from 4-12 carbons.

35. The method of claim 34 wherein the polyamide is nylon 12.

36. The method of claim 31 wherein the polyolefin of the solution contact layer is selected from the group consisting of homopolymers and copolymers of alpha-olefins containing from 2 to about 20 carbon atoms.

37. The method of claim 36 wherein the polyolefin of the solution contact layer is a homopolymer or a copolymer of an alpha-olefin having from 2 to about 10 carbons.

38. The method of claim 37 wherein the polyolefin is selected from the group consisting of ethylene copolymers, and butene-1 copolymers.

39. The method of claim 38 wherein the ethylene copolymer of the solution contact layer is an ethylene-butene-1 copolymer.

40. The method of claim 39 wherein the ethylene copolymer of the solution contact layer is produced using a metallocene catalyst.

41. The method of claim 32 wherein the tie layer is a polyolefin polymer or copolymer blended with a polyethylene copolymer grafted with a carboxylic acid anhydride or a carboxylic acid.

42. The method of claim 41 wherein the carboxylic acid anhydride is an unsaturated fused ring carboxylic acid anhydride.

43. The method of claim 42 wherein the carboxylic acid anhydride is a maleic anhydride.

44. The method of claim 31 wherein the low molecular weight water soluble fraction of the structure is less than 100 ppm as measured for a container having a surface area of 450 cm² and containing 250 ml of saline solution.

45. The method of claim 31 wherein the low molecular weight water soluble fraction of the structure is less than 10 ppm as measured for a container having a surface area of 450 cm² and containing 250 ml of saline solution.

46. The method of claim 31 wherein the solution contact layer is from about 3-8 mils thick, the core layer is from about 0.2-2.5 mils thick, the outer layer is from about 0.2-2.0 mils thick, and the tie layers are from 0.2-1.2 mils thick to define an asymmetrical structure about the core layer.

47. A multiple layer structure for fabricating medical products comprising:

a core layer having a plurality of core sublayers each of an ethylene vinyl alcohol copolymer having an ethylene content of about 25-45 mole percent;

a plurality of tie sublayers interposed between each set of adjacent core sublayers;

a solution contact layer of a polyolefin positioned on a first side of the core layer;

an outer layer positioned on a second side of the core layer opposite the solution contact layer, the outer layer being selected from the group consisting of polyamides, and polyesters; and

wherein the structure is produced in a cast coextrusion process essentially free of water soluble slip agents.

48. The multilayered structure of claim 47 wherein there are from about 2 to 10 core sublayers.

49. A multiple layer structure for fabricating medical products comprising:

a core layer of an ethylene vinyl alcohol copolymer having an ethylene content of about 25-45 mole percent;

a solution contact layer having three sublayers each of a polyolefin, the solution contact layer being positioned on a first side of the core layer;

an outer layer positioned on a second side of the core layer opposite the solution contact layer, the outer layer being selected from the group consisting of polyamides, and polyesters; and

wherein the structure is produced in a cast coextrusion process essentially free of water soluble slip agents.

50. The multilayered structure of claim 49 wherein the solution contact layer has a centrally disposed sublayer and two flanking sublayers, the centrally disposed sublayer has a lower water vapor transmission rate than that of the flanking sublayers of the solution contact layer.

51. The multilayered structure of claim 49 wherein the flanking solution contact sublayers are of an ultra-low density polyethylene and the centrally disposed solution contact sublayer is of a low-density polyethylene.