PECVD coated pharmaceutical packaging
An article or vessel is described including a vessel surface and a coating set comprising at least one tie coating, at least one barrier coating, and at least one pH protective coating. For example, the coating set can comprise a tie coating, a barrier coating, a pH protective coating and a second barrier coating; and in the presence of a fluid composition, the fluid contacting surface is the barrier coating or layer. The respective coatings can be applied by PECVD of a polysiloxane precursor. Such vessels can have a coated interior portion containing a fluid with a pH of 4 to 8. The barrier coating prevents oxygen from penetrating into the thermoplastic vessel, and the tie coating and pH protective coating together protect the barrier layer from the contents of the vessel. The second barrier coating is comparable to glass surface if needed.
1. A vessel comprising:
a thermoplastic wall having an interior surface enclosing a lumen;
a tie coating comprising SiOxCy or SiNxCy wherein x is from about 0.5 to about 2.4 and y is from about 0.6 to about 3, the tie coating having an interior surface facing the lumen and an outer surface facing the wall interior surface;
a barrier coating having an interior surface facing the lumen and an outer surface facing the interior surface of the tie coating, the barrier coating being effective to reduce the ingress of atmospheric gas into the lumen compared to a vessel without the barrier coating; and
a pH protective coating comprising SiOxCy or SiNxCy wherein x is from about 0.5 to about 2.4 and y is from about 0.6 to about 3, the pH protective coating having an interior surface facing the lumen and an outer surface facing the interior surface of the barrier coating, the passivation or pH protective coating being effective to decrease the dissolution rate of the barrier coating in the presence of a fluid composition having a pH between 5 and 9 in the lumen.
2. The vessel of claim 1 , in which the barrier coating comprises SiOx, in which x is between 1.5 and 2.9.
3. The vessel of claim 1 , in which the thermoplastic wall comprises or consists essentially of a polyolefin, a cyclic olefin polymer, a cyclic olefin copolymer, a polyester, a polycarbonate, polylactic acid, or a combination or copolymer of these.
4. The vessel of claim 1 , wherein the tie coating has an average thickness of from 5 to 200 nm.
5. The vessel of claim 1 , in which the silicon dissolution rate by a 50 mM potassium phosphate buffer diluted in water for injection, adjusted to pH 8 with concentrated nitric acid, and containing 0.2 wt. % polysorbate- 80 surfactant, from the vessel is less than 170 ppb/day.
6. The vessel of claim 1 , in which the silicon dissolution rate by a 50 mM potassium phosphate buffer diluted in water for injection, adjusted to pH 8 with concentrated nitric acid, and containing 0.2 wt. % polysorbate- 80 surfactant, from the vessel is less than 100 ppb/day.
7. The vessel of claim 1 , in which a fluid contained in the lumen having a pH greater than 5 removes the pH protective coating at a rate of 1 nm or less of pH protective coating thickness per 88 hours of contact with the fluid.
8. The vessel of claim 1 , in which in the presence of a fluid composition having a pH between 5 and 9 contained in the lumen, the calculated shelf life of the vessel is more than six months at a storage temperature of 4° C.
9. The vessel of claim 1 , wherein the rate of erosion of the pH protective coating, if directly contacted by a fluid composition having a pH of 8, is less than 20% the rate of erosion of the barrier coating, if directly contacted by the same composition under the same conditions.
10. The vessel of claim 1 , wherein an FTIR absorbance spectrum of the pH protective coating has a ratio greater than 0.75 between:
the maximum amplitude of the Si-O-Si symmetrical stretch peak between about 1000 and 1040 cm-1, and
the maximum amplitude of the Si-O-Si assymmetric stretch peak between about 1060 and about 1100 cm-1;
wherein the pH protective coating is at least coextensive with the barrier coating; and
wherein the rate of erosion of the pH protective coating, if directly contacted by a fluid composition having a pH of 8, is less than 20% the rate of erosion of the barrier coating, if directly contacted by the same composition under the same conditions.
11. The vessel of claim 1 , wherein an FTIR absorbance spectrum of the pH protective coating has a ratio greater than 0.75 between:
the maximum amplitude of the Si-O-Si symmetrical stretch peak between about 1000 and 1040 cm-1, and
the maximum amplitude of the Si-O-Si assymmetric stretch peak between about 1060 and about 1100 cm-1.
12. The vessel of claim 11 , wherein the FTIR absorbance spectrum of the pH protective coating has a ratio greater than 0.9 between:
the maximum amplitude of the Si-O-Si symmetrical stretch peak between about 1000 and 1040 cm-1, and
the maximum amplitude of the Si-O-Si assymmetric stretch peak between about 1060 and about 1100 cm-1.
13. The vessel of claim 11 , wherein the pH protective coating has an O-parameter of less than 0.4, measured with attenuated total reflection (ATR) as:
O
-
Parameter
=
Intensity
at
1253
cm
-
1
Maximum
intensity
in
the
range
1000
to
1100
cm
-
1
.
14. The vessel of claim 13 , wherein the pH protective coating has an N-parameter of less than 0.7, measured with attenuated total reflection (ATR) as:
N
-
Parameter
=
Intensity
at
840
cm
-
1
Intensity
at
799
cm
-
1.
15. The vessel of claim 1 , wherein the vessel is a syringe barrel, a cartridge, a pharmaceutical vial, or a blister package.
16. The vessel of claim 15 , wherein the vessel is a syringe barrel or cartridge.
17. The vessel of claim 15 , wherein the vessel is a pharmaceutical vial.
18. The vessel of claim 1 , wherein the pH protective coating is from 10 nm to 1000 nm thick.
19. The vessel of claim 18 , wherein the pH protective coating is from 50 to 500 nm thick.
20. The vessel of claim 1 , wherein the pH protective coating is at least coextensive with the barrier coating.
21. The vessel of claim 20 , wherein the pH protective coating is applied by PECVD.