Claims
- 1. An article of manufacture comprising:
an elastomeric substrate; and a plasma deposited polymeric coating on a portion of the elastomeric substrate, wherein the polymeric coating comprises: a crosslinked amorphous polymer represented by a formula selected from the group consisting of: (1) M1xCyHzOaNb wherein M1 is a metal selected from the group consisting of titanium, silicon, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein x ranges from 0 to 1, y ranges from 0 to 12, z ranges from 0 to 28, a ranges from 0 to 4, and b ranges from 0 to 4, subject to the proviso that at least one of M1 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M1 and H may not be exclusively present; and (2) M2cCdHeOfNg wherein M2 is a metal selected from the group consisting of titanium, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein c ranges from 0 to 1, d ranges from 0 to 12, e ranges from 0 to 28; f ranges from 0 to 4, and g ranges from 0 to 4, subject to the proviso that at least one of M2 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M2 and H may not be exclusively present; wherein the total residue extracted by a volume of water contacted with the polymeric coating is reduced by at least about 20% compared to the total residue extracted by an equivalent volume of water contacted with an elastomeric substrate that is not coated with the polymeric coating under substantially the same conditions of pressure and temperature.
- 2. The article of manufacture of claim 1, wherein the polymeric coating provides at least one of reduced extraction of leachable elastomer components by solutions and solvents; reduced outgassing of volatile elastomer components; reduced swelling by oil, water, or other solvents; reduced diffusion of gases and water vapor; and a reduced coefficient of friction to the elastomeric substrate.
- 3. The article of manufacture of claim 1, wherein particle generation measured by the turbidity of a water sample contacted with the polymeric coating is reduced by at least about 20% compared to the turbidity of a water sample contacted with an elastomeric substrate that is not coated with the polymeric coating under substantially the same conditions of pressure and temperature.
- 4. The article of manufacture of claim 1, wherein the swelling of the elastomer substrate exposed to a solvent is reduced by at least about 20% compared to the swelling of an elastomeric substrate that is not coated with the polymeric coating exposed to the solvent under substantially the same conditions of pressure and temperature.
- 5. The article of manufacture of claim 1, wherein the elastomeric substrate has a coefficient of friction that is at least about 12% less than the coefficient of friction of an elastomeric substrate that is not coated with the polymeric coating.
- 6. The article of manufacture of claim 1, wherein the elastomeric substrate has an associated transmission of water vapor or gases that is at least about 20% less than the transmission of water vapor or gases associated with an elastomeric substrate that is not coated with the polymeric coating tested under substantially the same conditions of pressure, temperature and time.
- 7. The article of manufacture of claim 1, wherein the polymeric coating has a thickness between about 50 Å and about 5 micrometers.
- 8. The article of manufacture of claim 1, wherein either of M1 or M2 is titanium.
- 9. The article of manufacture of claim 1, wherein the polymeric coating is essentially free of silicone oil.
- 10. The article of manufacture according to claim 1, wherein said polymeric coating is bonded to said substrate.
- 11. The article of manufacture according to claim 1, further comprising a lubricious hydrophobic layer present on said polymeric coating.
- 12. The article of manufacture according to claim 11, wherein said lubricious hydrophobic layer is formed from a hydrophobic organic lubricant selected from the group consisting of fluorocarbons, fatty acids, and fatty acid esters.
- 13. A pharmaceutical closure for a drug vial comprising:
a closure member having an elastomeric substrate; and a plasma deposited polymeric coating on a portion of the elastomeric substrate, wherein the polymeric coating comprises: a crosslinked amorphous polymer represented by a formula selected from the group consisting of: (1) M1xCyHzOaNb wherein M1 is a metal selected from the group consisting of titanium, silicon, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein x ranges from 0 to 1, y ranges from 0 to 12, z ranges from 0 to 28, a ranges from 0 to 4, and b ranges from 0 to 4, subject to the proviso that at least one of M1 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M1 and H may not be exclusively present; and (2) M2cCdHeOfNg wherein M2is a metal selected from the group consisting of titanium, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein c ranges from 0 to 1, d ranges from 0 to 12, e ranges from 0 to 28; f ranges from 0 to 4, and g ranges from 0 to 4, subject to the proviso that at least one of M2 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M2 and H may not be exclusively present; wherein the total residue extracted by a volume of water contacted with the polymeric coating is reduced by at least about 20% compared to the total residue extracted by an equivalent volume of water contacted with an elastomeric substrate that is not coated with the polymeric coating under substantially the same conditions of pressure and temperature.
- 14. A pharmaceutical closure of claim 13, wherein the elastomeric substrate has a coefficient of friction that is at least about 12% less than the coefficient of friction of an elastomeric substrate that is not coated with the polymeric coating.
- 15. A hypodermic syringe stopper comprising:
a stopper having an elastomeric substrate; and a plasma deposited polymeric coating on a portion of the elastomeric substrate, wherein the polymeric coating comprises: a crosslinked amorphous polymer represented by a formula selected from the group consisting of: (1) M1xCyHzOaNb wherein M1 is a metal selected from the group consisting of titanium, silicon, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein x ranges from 0 to 1, y ranges from 0 to 12, z ranges from 0 to 28, a ranges from 0 to 4, and b ranges from 0 to 4, subject to the proviso that at least one of M1 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M1 and H may not be exclusively present; and (2) M2cCdHeOfNg wherein M2is a metal selected from the group consisting of titanium, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein c ranges from 0 to 1, d ranges from 0 to 12, e ranges from 0 to 28; f ranges from 0 to 4, and g ranges from 0 to 4, subject to the proviso that at least one of M2 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M2 and H may not be exclusively present; wherein the total residue extracted by a volume of water contacted with the polymeric coating is reduced by at least about 20% compared to the total residue extracted by an equivalent volume of water contacted with an elastomeric substrate that is not coated with the polymeric coating under substantially the same conditions of pressure and temperature.
- 16. A hypodermic syringe stopper according to claim 15, wherein the elastomeric substrate has a coefficient of friction that is at least about 12% less than the coefficient of friction of an elastomeric substrate that is not coated with the polymeric coating.
- 17. A gasket comprising:
a gasket member having an elastomeric substrate; and a plasma deposited polymeric coating on a portion of the elastomeric substrate, wherein the polymeric coating comprises: a crosslinked amorphous polymer represented by a formula selected from the group consisting of: (1) M1xCyHzOaNb wherein M1 is a metal selected from the group consisting of titanium, silicon, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein x ranges from 0 to 1, y ranges from 0 to 12, z ranges from 0 to 28, a ranges from 0 to 4, and b ranges from 0 to 4, subject to the proviso that at least one of M1 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M1 and H may not be exclusively present; and (2) M2cCdHeOfNg wherein M2 is a metal selected from the group consisting of titanium, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein c ranges from 0 to 1, d ranges from 0 to 12, e ranges from 0 to 28; f ranges from 0 to 4, and g ranges from 0 to 4, subject to the proviso that at least one of M2 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M2 and H may not be exclusively present; wherein the total residue extracted by a volume of water contacted with the polymeric coating is reduced by at least about 20% compared to the total residue extracted by an equivalent volume of water contacted with an elastomeric substrate that is not coated with the polymeric coating under substantially the same conditions of pressure and temperature.
- 18. The gasket of claim 17, wherein the gasket member comprises an o-ring.
- 19. The gasket of claim 17, wherein the gasket member is configured to be incorporated into an inhaler for delivering a pharmaceutical compound to a mammal in need of treatment.
- 20. The gasket of claim 17, wherein the elastomeric substrate has a coefficient of friction that is at least about 12% less than the coefficient of friction of an elastomeric substrate that is not coated with the polymeric coating.
- 21. The gasket of claim 17, wherein the elastomeric substrate has an associated transmission of water vapor or gases that is at least about 20% less than the transmission of water vapor or gases associated with an elastomeric substrate that is not coated with the polymeric coating tested under substantially the same conditions of pressure, temperature and time.
- 22. A seal comprising:
a sealing member having an elastomeric substrate; and a plasma deposited polymeric coating on a portion of the elastomeric substrate, wherein the polymeric coating comprises: a crosslinked amorphous polymer represented by a formula selected from the group consisting of: (1) M1xCyHzOaNb wherein M1 is a metal selected from the group consisting of titanium, silicon, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein x ranges from 0 to 1, y ranges from 0 to 12, z ranges from 0 to 28, a ranges from 0 to 4, and b ranges from 0 to 4, subject to the proviso that at least one of M1 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M1 and H may not be exclusively present; and (2) M2cCdHeOfNg wherein M2 is a metal selected from the group consisting of titanium, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein c ranges from 0 to 1, d ranges from 0 to 12, e ranges from 0 to 28; f ranges from 0 to 4, and g ranges from 0 to 4, subject to the proviso that at least one of M2 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M2 and H may not be exclusively present; wherein the swelling of the elastomer substrate exposed to a solvent is reduced by at least about 20% compared to the swelling of an elastomeric substrate that is not coated with the polymeric coating exposed to the solvent under substantially the same conditions of pressure and temperature.
- 23. A seal according to claim 22, wherein the elastomeric substrate has a coefficient of friction that is at least about 12% less than the coefficient of friction of an elastomeric substrate that is not coated with the polymeric coating.
- 24. A seal according to claim 22, wherein the elastomeric substrate has an associated transmission of water vapor or gases that is at least about 20% less than the transmission of water vapor or gases associated with an elastomeric substrate that is not coated with the polymeric coating tested under substantially the same conditions of pressure, temperature and time.
- 25. A pharmaceutical delivery device comprising:
a drug container comprising:
a barrel for containing a pharmaceutical substance; a movable stopper situated within the barrel; and a blunt end having an opening through which the substance within the barrel can be expelled; wherein the stopper comprises: an elastomeric substrate; and a plasma deposited polymeric coating on a portion of the elastomeric substrate, wherein the polymeric coating comprises: a crosslinked amorphous polymer represented by a formula selected from the group consisting of: (1) M1xCyHzOaNb wherein M1 is a metal selected from the group consisting of titanium, silicon, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein x ranges from 0 to 1, y ranges from 0 to 12, z ranges from 0 to 28, a ranges from 0 to 4, and b ranges from 0 to 4, subject to the proviso that at least one of M1 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M1 and H may not be exclusively present; and (2) M2cCdHeOfNg wherein M2 is a metal selected from the group consisting of titanium, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein c ranges from 0 to 1, d ranges from 0 to 12, e ranges from 0 to 28; f ranges from 0 to 4, and g ranges from 0 to 4, subject to the proviso that at least one of M2 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M2 and H may not be exclusively present; wherein the total extractable residue of a volume of water contacted with the polymeric coating is reduced by at least about 20% compared to the total extractable residue of the same volume of water contacted with an elastomeric substrate that is not coated with the polymeric coating under substantially the same conditions of pressure and temperature.
- 26. The pharmaceutical delivery device of claim 25, wherein the elastomeric substrate has a coefficient of friction that is at least about 12% less than the coefficient of friction of an elastomeric substrate that is not coated with the polymeric coating.
- 27. The pharmaceutical delivery device of claim 25, wherein the drug container comprises a syringe.
- 28. The pharmaceutical delivery device of claim 25, wherein the pharmaceutical delivery device is essentially free of silicone oil.
- 29. A vial for storing medicament comprising:
a container comprising an open end with a radial rim portion surrounding the open end; and a stopper comprising a tubular portion inserted into the open end of the container and a generally planar rim portion which overlies the radial rim portion; wherein the stopper comprises: an elastomeric substrate; and a plasma deposited polymeric coating on a portion of the elastomeric substrate, wherein the polymeric coating comprises: a crosslinked amorphous polymer represented by a formula selected from the group consisting of: (1) M1xCyHzOaNb wherein M1 is a metal selected from the group consisting of titanium, silicon, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein x ranges from 0 to 1, y ranges from 0 to 12, z ranges from 0 to 28, a ranges from 0 to 4, and b ranges from 0 to 4, subject to the proviso that at least one of M1 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M1 and H may not be exclusively present; and (2) M2cCdHeOfNg wherein M2 is a metal selected from the group consisting of titanium, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein c ranges from 0 to 1, d ranges from 0 to 12, e ranges from 0 to 28; f ranges from 0 to 4, and g ranges from 0 to 4, subject to the proviso that at least one of M2or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M2 and H may not be exclusively present; wherein the total residue extracted by a volume of water contacted with the polymeric coating is reduced by at least about 20% compared to the total residue extracted by an equivalent volume of water contacted with an elastomeric substrate that is not coated with the polymeric coating under substantially the same conditions of pressure and temperature.
- 30. A vial according to claim 29, wherein the elastomeric substrate has a coefficient of friction that is at least about 12% less than the coefficient of friction of an elastomeric substrate that is not coated with the polymeric coating.
- 31. A vial according to claim 29, wherein the stopper is essentially free of silicone oil.
- 32. A pharmaceutical delivery device comprising:
a drug container comprising:
a container for containing a pharmaceutical substance and a propellant at a pressure greater than atmospheric pressure for delivering the pharmaceutical substance; a valve operatively connected to the container for dispensing a controlled dose of the propellant and pharmaceutical substance; wherein the valve comprises at least one seal comprising: an elastomeric substrate; and a plasma deposited polymeric coating on a portion of the elastomeric substrate, wherein the polymeric coating comprises: a crosslinked amorphous polymer represented by a formula selected from the group consisting of: (1) M1xCyHzOaNb wherein M1 is a metal selected from the group consisting of titanium, silicon, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein x ranges from 0 to 1, y ranges from 0 to 12, z ranges from 0 to 28, a ranges from 0 to 4, and b ranges from 0 to 4, subject to the proviso that at least one of M1 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M1 and H may not be exclusively present; and (2) M2cCdHeOfNg wherein M2is a metal selected from the group consisting of titanium, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein c ranges from 0 to 1, d ranges from 0 to 12, e ranges from 0 to 28; f ranges from 0 to 4, and g ranges from 0 to 4, subject to the proviso that at least one of M2 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M2 and H may not be exclusively present; wherein the total residue extracted by a volume of water contacted with the polymeric coating is reduced by at least about 20% compared to the total residue extracted by an equivalent volume of water contacted with an elastomeric substrate that is not coated with the polymeric coating under substantially the same conditions of pressure and temperature.
- 33. The pharmaceutical delivery device of claim 32, wherein the drug container comprises a nasal spray.
- 34. The pharmaceutical delivery device of claim 32, wherein the drug container comprises an inhaler.
- 35. The pharmaceutical delivery device of claim 32, wherein the valve is essentially free of silicone oil.
- 36. The pharmaceutical delivery device of claim 32, wherein the elastomeric substrate has a coefficient of friction that is at least about 12% less than the coefficient of friction of an elastomeric substrate that is not coated with the polymeric coating.
- 37. The pharmaceutical delivery device of claim 32, wherein the elastomeric substrate has an associated transmission of water vapor or gases that is at least about 20% less than the transmission of water vapor or gases associated with an elastomeric substrate that is not coated with the polymeric coating tested under substantially the same conditions of pressure, temperature and time.
- 38. A vacuum seal comprising:
a first closure member having an opening; a second closure member sized to cover the opening; and a sealing member for forming a connection seal between the first closure member and the second closure member, wherein the sealing member comprises: an elastomeric substrate; and a plasma deposited polymeric coating on a portion of the elastomeric substrate, wherein the polymeric coating comprises: a crosslinked amorphous polymer represented by a formula selected from the group consisting of: (1) M1xCyHzOaNb wherein M1 is a metal selected from the group consisting of titanium, silicon, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein x ranges from 0 to 1, y ranges from 0 to 12, z ranges from 0 to 28, a ranges from 0 to 4, and b ranges from 0 to 4, subject to the proviso that at least one of M1 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M1 and H may not be exclusively present; and (2) M2cCdHeOfNg wherein M2 is a metal selected from the group consisting of titanium, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein c ranges from 0 to 1, d ranges from 0 to 12, e ranges from 0 to 28; f ranges from 0 to 4, and g ranges from 0 to 4, subject to the proviso that at least one of M2 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating, except that M2 and H may not be exclusively present; wherein the elastomeric substrate has an associated transmission of water vapor or gases that is at least about 20% less than the transmission of water vapor or gases associated with an elastomeric substrate that is not coated with the polymeric coating tested under substantially the same conditions of pressure, temperature and time.
- 39. The vacuum seal of claim 38, wherein the sealing member comprises an o-ring.
- 40. The vacuum seal of claim 38, wherein the coating is essentially free of silicone oil.
- 41. The vacuum seal of claim 38, wherein the elastomeric substrate has a coefficient of friction that is at least about 12% less than the coefficient of friction of an elastomeric substrate that is not coated with the polymeric coating.
- 42. A method of forming a crosslinked amorphous polymer, said method comprising:
exposing a composition comprising at least one metal organic precursor to an energy source to form a energized precursor; promoting the energized precursor into an excited state to produce ionized materials; and depositing the ionized materials on a substrate such that the ionized materials form the crosslinked amorphous polymer represented by a formula selected from the group consisting of: (1) M1xCyHzOaNb wherein M1 is a metal selected from the group consisting of titanium, silicon, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein x ranges from 0 to 1, y ranges from 0 to 12, z ranges from 0 to 28, a ranges from 0 to 4, and b ranges from 0 to 4, subject to the proviso that at least one of M1 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating composition, except that M1 and H may not be exclusively present; and (2) M2cCdHeOfNg wherein M2 is a metal selected from the group consisting of titanium, tantalum, germanium, boron, zirconium, aluminum, hafnium, and yttrium, wherein c ranges from 0 to 1, d ranges from 0 to 12, e ranges from 0 to 28; f ranges from 0 to 4, and g ranges from 0 to 4, subject to the proviso that at least one of M2 or C must be present and at least one of C, H, O, or N must be present in said polymeric coating composition, except that M2 and H may not be exclusively present.
- 43. The method according to claim 42, wherein either of M1 or M2 is titanium.
- 44. The method according to claim 42, wherein the metal organic precursor is a monomer selected from the group consisting of silanes, siloxanes, silazanes,titanates, and mixures thereof.
- 45. The method according to claim 42, wherein the metal organic precursor comprises tetramethysilane.
- 46. The method according to claim 42, wherein the metal organic precursor comprises tetraisopropyl titaniate.
- 47. The method according to claim 42, wherein said step of promoting the energized precursor into an excited state to produce ionized materials comprises breaking down the monomer into atomic species, molecular species, or both.
- 48. The method according to claim 42, wherein said method is a plasma enhanced chemical vapor deposition method.
- 49. The method according to claim 42 further comprising:
adding a lubricous coating layer comprising a hydrophobic or hydrophilic organic lubricant selected from the group consisting of fluorocarbons, fatty acids, and fatty acid esters.
- 50. The method according to claim 49, wherein said lubricious coating layer is applied by one or more of dip, spray, or flow coating techniques.
RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Patent Application No. 60/297,676 filed on Jun. 12, 2001.
Provisional Applications (1)
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Number |
Date |
Country |
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60297676 |
Jun 2001 |
US |