Coated packaging
A vessel has an interior surface facing a lumen. The interior surface includes a tie coating or layer, a barrier coating or layer, and a pH protective coating or layer. The tie coating or layer can comprise SiO x C y or SiN x C y , where x is from about 0.5 to about 2.4 and y is from about 0.6 to about 3. The barrier coating or layer can comprise SiO x , wherein x is from 1.5 to 2.9. The barrier coating or layer reduces the ingress of atmospheric gas into the lumen. The pH protective coating or layer can comprise SiO x C y or SiN x C y , as well. In an embodiment, in the presence of a fluid composition contained in the lumen and having a pH between 5 and 9, the calculated shelf life of the package can be more than six months at a storage temperature of 4° C.
1. A vessel comprising:
a thermoplastic wall having an interior surface enclosing at least a portion of a lumen;
a tie coating or layer comprising SiO x C y H z or SiN x C y H z in which x is from 0.5 to 2.4 as measured by X-ray photoelectron spectroscopy (XPS), y is from 0.6 to 3 as measured by XPS, and z is from 2 to 9 as measured by Rutherford backscattering spectrometry (RBS), the tie coating or layer having an outer surface facing the interior surface of the thermoplastic wall and the tie coating or layer having an interior surface;
a barrier coating or layer of SiO x , in which x is from 1.5 to 2.9 as measured by XPS, the barrier coating or layer positioned between the interior surface of the tie coating or layer and the lumen; and
a pH protective coating or layer of SiO x C y H z , in which x is from 0.5 to 2.4 as measured by XPS, y is from 0.6 to 3 as measured by XPS, and z is from 2 to 9 as measured by RBS, positioned between the barrier coating or layer and the lumen, in which an FTIR absorbance spectrum of the pH protective coating or layer has a ratio greater than 0.9 between:
the maximum amplitude of the Si-O-Si symmetrical stretch peak between 1000 and 1040 cm −1 , and
the maximum amplitude of the Si-O-Si asymmetric stretch peak between 1060 and 1100 cm −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.
2. The vessel of claim 1 , in which at least one of the tie coating or layer, the barrier coating or layer, or the pH protective coating or layer is applied by plasma enhanced chemical vapor deposition (PECVD).
3. The vessel of claim 1 , which is a syringe barrel, a vial, a cartridge or a blister package.
4. The vessel of claim 1 , in which at least a portion of the thermoplastic wall comprises:
a polyolefin
a polyvinylalcohol
a polymethacrylate ether
a polyacrylic acid
a polyamide
a polyimide
a polysulfone
a polylactic acid
a cyclic olefin polymer or copolymer
a polyester or
a combination of a polyolefin and a polyester.
5. The vessel of claim 1 , in which, for at least one of the pH protective coating or layer or the tie coating or layer, x is from 1 to 2 as measured by XPS, y is from 0.6 to 1.5 as measured by XPS, and z is from 2 to 5 as measured by RBS.
6. The vessel of claim 1 , in which the pH protective coating or layer is from 10 to 1000 nm thick.
7. The vessel of claim 1 , in which the rate of erosion of the pH protective coating or layer, if directly contacted by a fluid contained in the lumen having a pH greater than 5, is less than 20% of the rate of erosion of the barrier coating or layer, if directly contacted by the same fluid under the same conditions.
8. The vessel of claim 1 , having a shelf life, while directly contacted by a fluid contained in the lumen having a pH greater than 5, of at least two years, based on storage of the vessel containing the fluid at 20° C.
9. The vessel of claim 1 , in which a fluid contained in the lumen having a pH greater than 5 removes the pH protective coating or layer at a rate of 1 nm or less of pH protective coating or layer thickness per 88 hours of contact with the fluid.
10. The vessel of claim 1 , wherein the pH protective coating or layer shows an O-Parameter measured with attenuated total reflection (ATR) of less than 0.4, measured as:
O
-
Parameter
=
Intensity
at
1253
cm
-
1
Maximum
intensity
in
the
range
from
1000
to
1100
cm
-
1
.
11. The vessel of claim 1 , in which the tie coating or layer has an average thickness from 5 to 200 nm.
12. The vessel of claim 1 , which is a prefilled syringe having a syringe barrel coated on its interior wall with the tie coating or layer, barrier coating or layer, and pH protective coating or layer, further having a plunger seated in the barrel and containing a pharmaceutical composition having a pH greater than 5 contained in the lumen, the prefilled syringe having a shelf life of at least six months.
13. A process for making a vessel according to claim 1 , the process comprising the steps:
forming a tie coating or layer;
forming a barrier coating or layer; and
forming a pH protective coating or layer positioned between the barrier coating or layer and the lumen,
the pH protective coating or layer and tie coating or layer together being effective to keep the barrier coating or layer at least substantially undissolved as a result of attack by a fluid contained in the lumen having a pH greater than 5 for a period of at least six months.