Biocompatible hydrophobic laminate with thermoplastic elastomer layer

• US 5,630,844 A
• Filed: 06/07/1995
• Issued: 05/20/1997
• Est. Priority Date: 06/07/1995
• Status: Expired due to Fees

• Current Assignee: Novamed Medical Products Manufacturing, Inc.
• Original Assignee: Novamed Medical Products Manufacturing, Inc.
• Inventors: Dogan, Aydin, Kredovski, Adam D., Kredovski, Kenneth C., Hayes, Thomas G.
• Primary Examiner(s): Weiss, John G.
• Assistant Examiner(s): CUDDIHY, FRANCIS KEVIN
• Application Number:
  US08/473,284
• Time in Patent Office: 713 Days
• Field of Search: 623/8, 623/11, 428/35.7, 428/412, 428/425.5, 428/447, 427/2.24, 427/2.3, 427/333, 427/336, 427/387, 427/393.5
• US Class Current: 623/8
• CPC Class Codes: A61F 2/12 Mammary prostheses and implants
• CPC Class Codes: A61F 2210/0071 thermoplastic
• CPC Class Codes: A61F 2240/001 Designing or manufacturing processes
• CPC Class Codes: A61L 27/16 obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 27/20 Polysaccharides
• CPC Class Codes: A61L 27/34 Macromolecular materials
• CPC Class Codes: A61L 29/041 obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 29/043 Polysaccharides
• CPC Class Codes: A61L 29/085 Macromolecular materials
• CPC Class Codes: B29C 41/14 Dipping a core B29C41/10 takes precedence
• CPC Class Codes: B32B 2250/40 Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
• CPC Class Codes: B32B 2250/42 Alternating layers, e.g. ABAB(C), AABBAABB(C)
• CPC Class Codes: B32B 2307/412 Transparent
• CPC Class Codes: B32B 2307/7246 Water vapor barrier
• CPC Class Codes: B32B 2307/73 Hydrophobic
• CPC Class Codes: B32B 2325/00 Polymers of vinyl-aromatic compounds, e.g. polystyrene
• CPC Class Codes: B32B 2367/00 Polyesters, e.g. PET, i.e. polyethylene terephthalate
• CPC Class Codes: B32B 2369/00 Polycarbonates
• CPC Class Codes: B32B 2375/00 Polyureas; Polyurethanes
• CPC Class Codes: B32B 25/00 Layered products comprising a layer of natural or synthetic rubber fibrous or filamentary layer made of a natural or synthetic rubber B32B5/02; particulate layer made of a natural or synthetic rubber B32B5/16; foamed layer made of a natural or synthetic rubber B32B5/18
• CPC Class Codes: B32B 25/04 : comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to a layer of a particular substance B32B9/043; next to a bituminous or tarry layer B32B11/044; next to a water setting substance layer B32B13/042; next to a metal layer B32B15/06; next to a glass layer B32B17/063; next to a layer formed of natural mineral fibres or particles B32B19/043; next to a wood layer B32B21/045; next to a cellulosic plastic layer B32B23/046
• CPC Class Codes: B32B 25/08 : of synthetic resin
• CPC Class Codes: B32B 25/20 : comprising silicone rubber
• CPC Class Codes: B32B 2535/00 : Medical equipment, e.g. bandage, prostheses or catheter
• CPC Class Codes: B32B 27/22 : using plasticisers
• CPC Class Codes: B32B 27/302 : comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
• CPC Class Codes: B32B 27/32 : comprising polyolefins comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30
• CPC Class Codes: B32B 27/365 : comprising polycarbonates
• CPC Class Codes: B32B 27/40 : comprising polyurethanes
• CPC Class Codes: B32B 3/04 : characterised by at least one layer folded at the edge, e.g. over another layer ; characterised by at least one layer enveloping or enclosing a material
• CPC Class Codes: C08L 53/00 : Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 : Polysiloxanes

Abstract

A biocompatible hydrophobic laminate. The laminate structure includes one layer of a rubber, such as silicone rubber, which is biocompatible with the inside of the body. The laminate structure further includes a hydrophobic layer or membrane formed of a thermoplastic elastomer such as a styrene triblock copolymer. The triblock copolymer may contain styrene endblocks with an elastomeric midblock such as polyisoprene, polybutadiene, polyisobutylene, and poly(ethylene-co-butylene). The laminate structure may be utilized for structures to be introduced into the body, such as for a breast prosthesis shell or a coating for a catheter.

Claims

1. A biocompatible hydrophobic laminate structure for enveloping matter, the laminate structure and matter to be introduced into a host'"'"'s body, the laminate structure comprising:

a) at least one rubber layer which is biocompatible with an inside portion of the body or body tissue or body fluid;

b) a hydrophobic, water vapor barrier membrane laminated on each rubber layer to minimize the permeation of moisture through the laminate structure;

c) with the hydrophobic water vapor barrier membrane being isolated from the inside portion of the body or body tissue or body fluid by the at least one rubber layer; and

d) with the hydrophobic membrane comprising a thermoplastic elastomer which is substantially impermeable to water vapor and which is present in the membrane in a concentration effective such that the membrane also is substantially impermeable to water vapor and such that, when formed as an implantable water-based fluid enveloping structure, said structure prevents substantial permeation of the water vapor contained therein, barring rupture of said implantable structure.

2. The biocompatible laminate structure of claim 1 wherein the thermoplastic elastomer comprises a block copolymer.

3. The biocompatible laminate structure of claim 2 wherein the block copolymer is selected from the group consisting of block copolymers having the structure A-B-A and (A-B)_n where A is a thermoplastic block and B is an elastomeric block.

4. The biocompatible laminate structure of claim 3 wherein A is polystyrene.

5. The biocompatible laminate structure of claim 3 wherein B is selected from the group consisting of olefinic, vinyl, and dienyl polymers.

6. The biocompatible laminate structure of claim 3 wherein B is selected from the group consisting of polyisoprene, polybutadiene, polyisobutylene, and ethylene/butylene polymers.

7. The biocompatible laminate structure of claim 3 wherein A is polystyrene and B is selected from the group consisting of polyisoprene, polybutadiene, polyisobutylene, and ethylene/butylene polymers.

8. The biocompatible laminate structure of claim 3 wherein A is selected from the group consisting of polystyrene, poly(methyl methacrylate), polypropylene, poly(α

-methylstyrene), polysulfone, polyethylene, polyester, polyarylester, and polyarylether and wherein B is selected from the group consisting of polyisoprene, polybutadiene, polyisobutylene, and poly(ethylene-co-butylene).

9. The biocompatible laminate structure of claim 3 wherein B is thermodynamically incompatible with A.

10. The biocompatible laminate structure of claim 1 wherein the thermoplastic elastomer comprises an ethylene-propylene based copolymer.

11. The biocompatible laminate structure of claim 10 wherein the thermoplastic elastomer comprises an ethylene-propylene multi-arm copolymer.

12. The biocompatible laminate structure of claim 1 wherein the thermoplastic elastomer comprises an ethylene-propylene based copolymer and a styrene block copolymer.

13. The biocompatible laminate structure of claim 1 wherein the thermoplastic elastomer includes an H₂ O permeability coefficient at about that of polyisoprene or less as measured by ASTM E 96-80 (Procedure E).

14. The biocompatible laminate structure of claim 1 wherein the hydrophobic membrane further comprises a resin and a plasticizer mixed in with the thermoplastic elastomer.

15. The biocompatible laminate structure of claim 1 wherein the hydrophobic membrane further comprises a hydrochlorocarbon based polymer mixed in with the thermoplastic elastomer.

16. The biocompatible laminate structure of claim 15 wherein the hydrochlorocarbon based polymer is selected from the group consisting of vinylidene chloride and polychloroprene.

17. The biocompatible laminate structure of claim 15 wherein the hydrophobic membrane comprises a composite structure of at least one polyolefin and at least one hydrochlorocarbon.

18. The biocompatible laminate structure of claim 1 wherein the thermoplastic elastomer is selected from the group consisting of thermoplastic olefins, thermoplastic vulcanizates, thermoplastic copolyester and thermoplastic copolyamide where such thermoplastic elastomers have hydrophobic, water vapor barrier properties with an H₂ O permeability coefficient at about that of polyisoprene or less as measured by ASTM E 96-80 (Procedure E).

19. The biocompatible laminate structure of claim 1 wherein the biocompatible rubber layer is selected from the group consisting of silicone rubbers and polyurethane.

20. The biocompatible laminate structure of claim 19 wherein the biocompatible rubber layer comprises silicone rubber.

21. The biocompatible laminate structure of claim 1 and further comprising another rubber layer, with the hydrophobic membrane being laminated between the rubber layers.

22. The biocompatible laminate structure of claim 21, further comprising at least one more of said hydrophobic membrane and at least one more rubber layer such that one rubber layer is sandwiched between two hydrophobic membranes which in turn are sandwiched between two rubber layers.

23. The laminate structure of claim 1 having a tensile strength of at least 900 pounds per square inch and a tear resistance of at least 100 pounds per inch, and being elongatable up to 1000% without delamination.

24. The laminate structure of claim 1 wherein the laminate structure is transparent.

25. The biocompatible laminate structure of claim 1 wherein the thermoplastic elastomer is less permeable to water vapor than the at least one rubber layer by at least one order of magnitude when measured in accordance with ASTM E 96-80 (Procedure E) in units of 10¹⁰ ×

cc (at STP)×

cm/sq cm×

sec×

cm Hg.

26. A breast prosthesis shell comprising:

a) at least one elastomeric layer having outer and inner surfaces, the outer surface of the at least one elastomeric layer being biocompatible with an inside portion of a host'"'"'s body; and

b) a hydrophobic, water vapor barrier membrane on the inner surface of each elastomeric layer to minimize the permeation of moisture through the breast prosthesis shell, with the hydrophobic membrane being isolated from the inside portion of the body or body tissue or body fluid by the at least one elastomeric layer, the hydrophobic membrane comprising a thermoplastic elastomer which is substantially impermeable to water vapor such that, when the shell is formed as an implantable water-based fluid enveloping structure, said structure prevents substantial permeation of the water vapor contained therein, barring rupture of said implantable structure.

27. A breast prosthesis shell comprising:

a) a pair of silicone elastomer layers; and

b) a hydrophobic, water vapor barrier membrane laminated between the silicone elastomer layers so as to be isolated from body tissue or filling for the shell and comprising a styrene block thermoplastic elastomer or a styrene derivative block thermoplastic elastomer which is substantially impermeable to water vapor such that, when the shell is formed as an implantable water-based fluid enveloping structure, said structure prevents substantial permeation of the water vapor contained therein, barring rupture of said implantable structure.

28. A breast prosthesis comprising:

a shell with an outer surface which is compatible with an inside portion of a host'"'"'s body, a water-based filling material for the shell, closure means on the shell for sealing the water-based filling material in the shell, and a hydrophobic, water vapor barrier membrane laminated on the shell inwardly of the outer surface with the water vapor barrier membrane being isolated from the inside portion of the body or body tissue or body fluid by the shell, and comprising a thermoplastic elastomer which is substantially impermeable to water vapor such that permeation of water vapor through the membrane from the water-based filling material or body is minimized and such that, when the prosthesis is formed as an implantable water-based fluid enveloping structure, said structure prevents substantial permeation of the water vapor contained therein, barring rupture of said implantable structure.

29. A biocompatible hydrophobic laminate structure for enveloping matter, the laminate structure and matter to be introduced into a host'"'"'s body, the laminate structure comprising:

a) at least one rubber layer which is biocompatible with the inside of the body or body tissue or body fluid; and

b) a hydrophobic, water vapor barrier membrane laminated on each rubber layer to minimize the permeation of moisture through the laminate structure, with the hydrophobic membrane being isolated from the inside portion of the body or body tissue or body fluid by the at least one rubber layer, the hydrophobic membrane comprising a thermoplastic elastomer comprised of a block copolymer selected from the group consisting of block copolymers having the structure A-B-A and (A-B)_n where A is a thermoplastic block and B is an elastomeric block, wherein B comprises a hydrocarbon, and wherein the block copolymer is substantially impermeable to water vapor such that, when formed as an implantable water-based fluid enveloping structure, said structure prevents substantial permeation of the water vapor contained therein barring rupture of said implantable structure.

30. A biocompatible hydrophobic laminate structure for enveloping matter, the laminate structure and matter to be introduced into a host'"'"'s body, the laminate structure comprising:

a) at least one rubber layer which is biocompatible with an inside of the body or body tissue or body fluid, with the at least one rubber layer comprising a rubber selected from the group consisting of silicone and polyurethane;

b) a hydrophobic, water vapor barrier membrane laminated on each rubber layer to minimize permeation of moisture through the laminate structure;

c) with the hydrophobic, water vapor barrier membrane being isolated from the inside portion of the body or body tissue or body fluid by the at least one rubber layer,

d) with the hydrophobic, water vapor barrier membrane comprising a thermoplastic elastomer; and

e) with the thermoplastic elastomer being substantially less permeable to water vapor than either the silicone or polyurethane of each rubber layer such that, when formed as an implantable water-based fluid enveloping structure, said structure prevents substantial permeation of the water vapor contained therein, barring rupture of said implantable structure.

31. The biocompatible hydrophobic laminate structure of claim 30 wherein the thermoplastic elastomer is less permeable to water vapor than one of the silicone and polyurethane of each rubber layer by at least one order of magnitude when measured in accordance with ASTM E 96-80 (Procedure E) in units of 10¹⁰ ×

cc (at STP)×

cm/sq cm×

see×

cm Hg.

32. A biocompatible hydrophobic laminate structure for enveloping matter, the laminate structure and matter to be introduced into a host'"'"'s body, the laminate structure comprising:

a) at least one rubber layer which is biocompatible with an inside of the body or body tissue or body fluid, with each rubber layer optionally comprising polyurethane;

b) a hydrophobic, water vapor barrier membrane laminated on each rubber layer to minimize permeation of moisture through the laminate structure;

c) with the hydrophobic, water vapor barrier membrane being isolated from the inside portion of the body or body tissue or body fluid by the at least one rubber layer;

d) with the hydrophobic, water vapor barrier membrane comprising a thermoplastic elastomer; and

e) with the thermoplastic elastomer being substantially less permeable to water vapor than polyurethane such that, when formed as an implantable water-based fluid enveloping structure, said structure prevents substantial permeation of the water vapor contained therein, barring rupture of said implantable structure.