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US-12623813-B2 - Passivation, pH protective or lubricity coating for pharmaceutical package, coating process and apparatus

US12623813B2US 12623813 B2US12623813 B2US 12623813B2US-12623813-B2

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 O 2 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 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.

Inventors

  • John T. Felts
  • Thomas E. Fisk
  • Robert S. Abrams
  • John Ferguson
  • Jonathan R. Freedman
  • Robert J. Pangborn
  • Peter J. Sagona
  • Christopher Weikart

Assignees

  • SIO2 MEDICAL PRODUCTS, INC.

Dates

Publication Date
20260512
Application Date
20231220

Claims (20)

  1. 1 . An article comprising: a wall having a surface; a barrier coating or layer of SiOx, wherein x is from 1.5 to 2.9, from 2 to 1000 nm thick, the barrier coating or layer of SiOx having an outer surface facing the wall surface, the barrier coating or layer being effective to reduce the ingress of atmospheric gas through the wall compared to an uncoated wall; and a pH protective coating of SiOxCy wherein x is from about 0.5 to about 2.4 and y is from about 0.6 to about 3, on the barrier coating or layer, the pH protective coating being formed by chemical vapor deposition of a precursor selected from a a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, a silatrane, a silquasilatrane, a silproatrane, or a combination of any two or more of these precursors; in which 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 asymmetric stretch peak between about 1060 and about 1100 cm −1 ; and in which 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% of the rate of erosion of the barrier coating or layer, if directly contacted by the fluid composition under the same conditions.
  2. 2 . The article of claim 1 , in which at least a portion of the wall comprises or consists essentially of a polyolefin, a cyclic olefin polymer, a cyclic olefin copolymer, a polyester, and polycarbonate, or polylactic acid.
  3. 3 . The article of claim 1 , wherein the barrier coating is from 4 nm to 500 nm thick.
  4. 4 . The article of claim 1 , in which the pH protective coating is between 10 and 1000 nm thick.
  5. 5 . The article of claim 1 , in which the pH protective coating is coextensive with the barrier coating or layer.
  6. 6 . The article of claim 1 , in which the calculated shelf life (total Si/Si dissolution rate) is more than 1 year.
  7. 7 . The article of claim 1 , wherein the pH protective coating is applied by PECVD of a precursor feed comprising a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, or any combination of two or more of these precursors.
  8. 8 . The article of claim 7 , in which the precursor feed further comprises oxygen.
  9. 9 . The article of claim 1 , in which the fluid composition removes the pH protective coating at a rate of 1 nm or less of pH protective coating thickness per 44 hours of contact.
  10. 10 . The article of claim 9 , in which the fluid composition removes the pH protective coating at a rate of 1 nm or less of pH protective coating thickness per 88 hours of contact.
  11. 11 . The article of claim 1 , wherein the pH protective 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 ⁢ ⁢ 1000 ⁢ to ⁢ 1100 ⁢ cm - 1 .
  12. 12 . The article of claim 11 , wherein the pH protective layer shows an N-Parameter measured with attenuated total reflection (ATR) of less than 0.7, measured as: N - Parameter = Intensity ⁢ at ⁢ 840 ⁢ cm - 1 Intensity ⁢ at ⁢ 799 ⁢ cm - 1 .
  13. 13 . An article comprising: a wall having a surface; a barrier coating or layer of SiOx, wherein x is from 1.5 to 2.9, from 2 to 1000 nm thick, the barrier coating or layer of SiOx having an outer surface facing the wall surface, the barrier coating or layer being effective to reduce the ingress of atmospheric gas through the wall compared to an uncoated wall; and a pH protective coating of SiOxCy wherein x is from about 0.5 to about 2.4 and y is from about 0.6 to about 3, on the barrier coating or layer, the pH protective coating being formed by chemical vapor deposition of a precursor selected from a a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, a silatrane, a silquasilatrane, a silproatrane, or a combination of any two or more of these precursors; in which the rate of erosion of the passivation layer or pH protective coating, if directly contacted by a fluid composition having a pH at some point between 5 and 9, is less than the rate of erosion of the barrier coating or layer, if directly contacted by the fluid composition; and in which 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 asymmetric stretch peak between about 1060 and about 1100 cm −1 .
  14. 14 . The article of claim 13 , in which an FTIR absorbance spectrum of the pH protective coating has a ratio of at least 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 asymmetric stretch peak between about 1060 and about 1100 cm −1 .
  15. 15 . The article of claim 13 , wherein the rate of erosion of the pH protective coating, if directly contacted by the fluid composition having a pH of 8, is less than 20% of the rate of erosion of the barrier coating or layer, if directly contacted by the fluid composition under the same conditions.
  16. 16 . The article of claim 13 , in which the pH protective coating is coextensive with the barrier coating or layer.
  17. 17 . The article of claim 13 , in which the fluid composition removes the pH protective coating at a rate of 1 nm or less of pH protective coating thickness per 44 hours of contact.
  18. 18 . The article of claim 17 , in which the fluid composition removes the pH protective coating at a rate of 1 nm or less of pH protective coating thickness per 88 hours of contact.
  19. 19 . The article of claim 13 , wherein the pH protective 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 ⁢ ⁢ 1000 ⁢ to ⁢ 1100 ⁢ cm - 1 .
  20. 20 . The article of claim 19 , wherein the pH protective layer shows an N-Parameter measured with attenuated total reflection (ATR) of less than 0.7, measured as: N - Parameter = Intensity ⁢ at ⁢ 840 ⁢ cm - 1 Intensity ⁢ at ⁢ 799 ⁢ cm - 1 .

Description

This application is a continuation of U.S. patent application Ser. No. 17/988,450, filed on Nov. 16, 2022, which is a continuation of U.S. patent application Ser. No. 17/484,944, filed Sep. 24, 2021, which is a continuation of U.S. patent application Ser. No. 16/806,589, filed Mar. 2, 2020, which is a continuation of U.S. patent application Ser. No. 16/226,463, filed Dec. 19, 2018, which is a division of U.S. patent application Ser. No. 14/357,418, filed May 9, 2014 as a national phase entry of PCT/US2012/064489, filed on Nov. 9, 2012, and which claims priority to U.S. Provisional Application Ser. Nos. 61/558,885, filed Nov. 11, 2011; 61/636,377, filed Apr. 20, 2012; and 61/645,003, filed May 9, 2012; all are incorporated herein by reference in their entirety. U.S. Provisional Ser. No. 61/177,984 filed May 13, 2009; 61/222,727, filed Jul. 2, 2009; 61/213,904, filed Jul. 24, 2009; 61/234,505, filed Aug. 17, 2009; 61/261,321, filed Nov. 14, 2009; 61/263,289, filed Nov. 20, 2009; 61/285,813, filed Dec. 11, 2009; 61/298,159, filed Jan. 25, 2010; 61/299,888, filed Jan. 29, 2010; 61/318,197, filed Mar. 26, 2010; 61/333,625, filed May 11, 2010; 61/413,334, filed Nov. 12, 2010; Ser. No. 12/779,007, filed May 12, 2010, now U.S. Pat. No. 7,985,188; International Application PCT/US11/36097, filed May 11, 2011; U.S. Ser. No. 61/558,885, filed Nov. 11, 2011; U.S. Ser. No. 61/636,377, filed Apr. 20, 2012; U.S. Ser. No. 61/645,003, filed May 9, 2012; and U.S. Ser. No. 61/716,381, filed Oct. 19, 2012; are all incorporated here by reference in their entirety. Also incorporated by reference in their entirety are the following European patent applications: EP10162755.2 filed May 12, 2010; EP10162760.2 filed May 12, 2010; EP10162756.0 filed May 12, 2010; EP10162758.6 filed May 12, 2010; EP10162761.0 filed May 12, 2010; and EP10162757.8 filed May 12, 2010. FIELD OF THE INVENTION The present invention relates to the technical field of coated surfaces, for example interior surfaces of pharmaceutical packages or other vessels for storing or other contact with fluids. Examples of suitable fluids include foods or biologically active compounds or body fluids, for example blood. The present invention also relates to a pharmaceutical package or other vessel and to a method for coating an inner or interior surface of a pharmaceutical package or other vessel. The present invention also relates more generally to medical devices, including devices other than packages or vessels, for example catheters. The present disclosure also relates to improved methods for processing pharmaceutical packages or other vessels, for example multiple identical pharmaceutical packages or other vessels used for pharmaceutical preparation storage and delivery, venipuncture and other medical sample collection, and other purposes. Such pharmaceutical packages or other vessels are used in large numbers for these purposes, and must be relatively economical to manufacture and yet highly reliable in storage and use. BACKGROUND OF THE INVENTION One important consideration in manufacturing pharmaceutical packages or other vessels for storing or other contact with fluids, for example vials and pre-filled syringes, is that the contents of the pharmaceutical package or other vessel desirably will have a substantial shelf life. During this shelf life, it can be important to isolate the material filling the pharmaceutical package or other vessel from the vessel wall containing it, or from barrier coatings or layers or other functional layers applied to the pharmaceutical package or other vessel wall to avoid leaching material from the pharmaceutical package or other vessel wall, barrier coating or layer, or other functional layers into the prefilled contents or vice versa. Since many of these pharmaceutical packages or other vessels are inexpensive and used in large quantities, for certain applications it will be useful to reliably obtain the necessary shelf life without increasing the manufacturing cost to a prohibitive level. For decades, most parenteral therapeutics have been delivered to end users in Type I medical grade borosilicate glass vessels such as vials or pre-filled syringes. The relatively strong, impermeable and inert surface of borosilicate glass has performed adequately for most drug products. However, the recent advent of costly, complex and sensitive biologics as well as such advanced delivery systems as auto injectors has exposed the physical and chemical shortcomings of glass pharmaceutical packages or other vessels, including possible contamination from metals, flaking, delamination, and breakage, among other problems. Moreover, glass contains several components which can leach out during storage and cause damage to the stored material. In more detail, borosilicate pharmaceutical packages or other vessels exhibit a number of drawbacks. Glass is manufactured from sand containing a heterogeneous mixture of many elements (silicon, oxygen, boron, aluminum