Passivation, pH protective or lubricity coating for pharmaceutical package, coating process and apparatus

• US 10,189,603 B2
• Filed: 11/09/2012
• Issued: 01/29/2019
• Est. Priority Date: 11/11/2011
• Status: Active Grant

• Current Assignee: SiO2 Medical products Inc.
• Original Assignee: SiO2 Medical products Inc.
• Inventors: Felts, John T., Fisk, Thomas E., Abrams, Robert S., Ferguson, John, Freedman, Jonathan R., Pangborn, Robert J., Sagona, Peter J., Weikart, Christopher
• Primary Examiner(s): Miggins, Michael C
• Application Number:
  US14/357,418
• Publication Number:
  US 20150021339A1
• Time in Patent Office: 2,272 Days
• CPC Class Codes: A61J 1/05 for collecting, storing or administering blood, plasma or medical fluids multiple bags systems for separating or storing blood components A61M1/0209; Infusion or perfusion containers
• CPC Class Codes: A61M 2005/3109 Caps sealing the needle bore by use of, e.g. air-hardening adhesive, elastomer or epoxy resin
• CPC Class Codes: A61M 2005/3131 specially adapted for improving sealing or sliding
• CPC Class Codes: A61M 5/3129 Syringe barrels A61M5/3205 and A61M5/50 take precedence
• CPC Class Codes: B65D 25/04 Partitions
• CPC Class Codes: B65D 25/14 Linings or internal coatings of containers made by folding or erecting blanks made of paper B65D5/56 ; linings for domestic water storage heaters F24H1/183
• CPC Class Codes: C23C 16/045 Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
• CPC Class Codes: C23C 16/30 Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
• CPC Class Codes: C23C 16/36 Carbonitrides
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/507 using external electrodes, e.g. in tunnel type reactors

Abstract

A method for providing a passivation layer or pH protective coating on a substrate surface by PECVD is provided, the method comprising generating a plasma from a gaseous reactant comprising polymerizing gases. The lubricity, passivation, pH protective, hydrophobicity, and/or barrier properties of the passivation layer or pH protective coating are set by setting the ratio of the O₂ to the organosilicon precursor in the precursor feed, and/or by setting the electric power used for generating the plasma. In particular, a passivation layer or pH protective coating made by the method is provided. Pharmaceutical packages coated by the method and the use of such packages protecting a composition contained in the vessel against mechanical and/or chemical effects of the surface of the package without a passivation layer or pH protective coating material are also provided.

Claims

1. A filled package comprising:

a vessel having a lumen defined at least in part by a wall, the wall having an interior surface facing the lumen and an outer surface;

a barrier coating or layer of SiO_x, wherein x is from 1.5 to 2.9, from 2 to 1000 nm thick, the barrier coating or layer of SiO_x having an interior surface facing the lumen and an outer surface facing the wall interior surface, the barrier coating or layer being effective to reduce the ingress of atmospheric gas into the lumen compared to an vessel without a barrier coating or layer;

a passivation layer or pH protective coating of SiO_xC_y or SiN_xC_y wherein x is from about 0.5 to about 2.4 and y is from about 0.6 to about 3, the passivation layer or pH protective coating having an interior surface facing the lumen and an outer surface facing the interior surface of the barrier coating or layer, the passivation layer or pH protective coating being effective to increase the calculated shelf life of the package (total Si/Si dissolution rate); and

a fluid composition contained in the lumen and having a pH between 4 and 10;

wherein the calculated shelf life of the package is more than six months at a storage temperature of 4°

C.; and

wherein an FTIR absorbance spectrum of the passivation layer or pH protective coating has a ratio greater than 0.75 and at most 1.7, between the maximum amplitude of the Si—

O—

Si symmetrical stretch peak between about 1000 and 1040 cm<sup>−

1</sup>, and the maximum amplitude of the Si—

O—

Si asymmetric stretch peak between about 1060 and about 1100 cm<sup>−

1</sup>.

2. The filled package of claim 1, in which at least a portion of the wall of the vessel comprises or consists essentially of a polyolefin, a cyclic olefin polymer, a cyclic olefin copolymer, a polyester, a polycarbonate, polylactic acid, glass, or a combination or copolymer of these.

3. The filled package of claim 1, in which the vessel comprises a syringe barrel, a cartridge, a vial, or a blister package.

4. The filled package of claim 1, in which the barrier coating or layer is from 10 nm to 300 nm thick.

5. The filled package of claim 1, in which the passivation layer or pH protective coating is applied by PECVD of a precursor feed comprising a linear siloxane, a linear silazane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, a monocyclic silazane, a polycyclic silazane, a polysilsesquiazane, a silatrane, a silquasilatrane, a silproatrane, an azasilatrane, an azasilquasiatrane, an azasilproatrane, or a combination of any two or more of these precursors.

6. The filled package of claim 1, in which the passivation layer or pH protective coating as applied is between 100 and 700 nm thick.

7. The filled package of claim 1, in which the rate of erosion of the passivation layer or pH protective coating, if directly contacted by a fluid composition having a pH of 8, is from 5% to 20%, of the rate of erosion of the barrier coating or layer, if directly contacted by the same fluid composition under the same conditions.

8. The filled package of claim 1, in which the passivation layer or pH protective coating is at least coextensive with the barrier coating or layer.

9. The filled package of claim 1, having a minimum shelf life, after the invention is assembled, of at least two years, wherein the shelf life is determined at 4°

C.

10. The filled package of claim 1, in which the fluid composition removes the passivation layer or pH protective coating at a rate of 1 nm or less of passivation layer or pH protective coating thickness per 44 hours of contact.

11. The filled package 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.

12. The filled package of claim 1, in which the total silicon content of the passivation layer or pH protective coating and barrier coating or layer, upon dissolution into 0.1 N potassium hydroxide aqueous solution at 40°

C. from the vessel, is less than 66 ppm.

13. The filled package of claim 1, in which the calculated shelf life (total Si/Si dissolution rate) is more than 2 years and less than 5 years.

14. The filled package of claim 1, in which the passivation layer or pH protective coating is applied by PECVD at a power level of from 1 to 250 W.

15. The filled package of claim 1, in which the ratio of the electrode power to the plasma volume is from 6 W/ml to 60 W/ml.

16. The filled package of claim 1, in which the calculated shelf life (total Si/Si dissolution rate) is less than 5 years.

17. The filled package of claim 5, in which the precursor feed further comprises an oxidizing gas.

18. The filled package of claim 17, in which the precursor feed further comprises a noble gas.

19. The filled package of claim 18, in which the precursor feed comprises:

from 0.5 to 10 standard volumes of an organosilicon precursor;

from 0.1 to 10 standard volumes of an oxidizing gas; and

from 1 to 100 sccm of a carrier gas.

20. The filled package of claim 1, in which the passivation layer or pH protective coating is effective to provide a lower frictional resistance than the uncoated interior surface.

21. The filled package of claim 20 wherein the frictional resistance is reduced by at least 45%, in comparison to the uncoated interior surface.

22. The filled package of claim 20, in which the passivation layer or pH protective coating is effective to reduce the frictional resistance between a portion of the wall contacted by the fluid composition and a relatively sliding part after the invention is assembled, wherein the filled package is a syringe comprising a syringe barrel and the relatively sliding part, wherein the wall defines at least a portion of the syringe barrel and the relatively sliding part comprises a plunger tip, piston, stopper, or seal.