Barrier coatings for elastomeric materials

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.

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.

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.

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.

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.

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.

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.

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.

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.