Syringe with PECVD lubricity layer

• US 10,537,273 B2
• Filed: 07/08/2019
• Issued: 01/21/2020
• Est. Priority Date: 05/13/2009
• 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.
• Primary Examiner(s): Proctor, Cachet I
• Application Number:
  US16/504,636
• Publication Number:
  US 20190328299A1
• Time in Patent Office: 197 Days
• Field of Search: None
• CPC Class Codes: A61B 5/150206 Construction or design features not otherwise provided for; manufacturing or production; packages; sterilisation of piercing element, piercing device or sampling device
• CPC Class Codes: A61B 5/154 Devices using pre-evacuated means
• CPC Class Codes: A61L 2400/10 Materials for lubricating medical devices
• CPC Class Codes: A61L 2420/02 Methods for coating medical devices
• CPC Class Codes: A61L 2420/08 Coatings comprising two or more layers
• CPC Class Codes: A61L 31/088 Other specific inorganic materials not covered by A61L31/084 or A61L31/086
• CPC Class Codes: A61L 31/10 Macromolecular materials
• CPC Class Codes: A61L 31/14 Materials characterised by their function or physical properties , e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
• CPC Class Codes: B05C 13/00 Means for manipulating or holding work, e.g. for separate articles B05C1/0821 takes precedence
• CPC Class Codes: B05C 13/025 relatively small cylindrical objects, e.g. cans, bottles
• CPC Class Codes: B23Q 7/04 by means of grippers B23Q7/1494 takes precedence
• CPC Class Codes: B23Q 7/1494 using grippers
• CPC Class Codes: C23C 16/045 Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/458 characterised by the method used for supporting substrates in the reaction chamber
• CPC Class Codes: C23C 16/50 using electric discharges generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34
• CPC Class Codes: C23C 16/505 using radio frequency discharges
• CPC Class Codes: C23C 16/52 Controlling or regulating the coating process C23C16/45557, C23C16/279 take precedence
• CPC Class Codes: C23C 16/54 Apparatus specially adapted for continuous coating
• CPC Class Codes: G01N 15/082 Investigating permeability by forcing a fluid through a sample
• CPC Class Codes: G01N 23/2273 : Measuring photoelectron spectrum, e.g. electron spectroscopy for chemical analysis [ESCA] or X-ray photoelectron spectroscopy [XPS]
• CPC Class Codes: G01N 30/7206 : interfaced to gas chromatograph interfaces in general for introducing or extracting samples to be analysed with specially adapted mass spectrometer, see H01J49/04
• CPC Class Codes: G01N 33/00 : Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
• CPC Class Codes: G01N 33/0096 : Testing material properties on thin layers or coatings
• CPC Class Codes: Y10T 428/13 : Hollow or container type article [e.g., tube, vase, etc.]
• CPC Class Codes: Y10T 428/1383 : Vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit is sandwiched between layers [continuous layer]

Abstract

Methods for processing a vessel, for example to provide a gas barrier or lubricity, are disclosed. First and second PECVD or other vessel processing stations or devices and a vessel holder comprising a vessel port are provided. An opening of the vessel can be seated on the vessel port. The interior surface of the seated vessel can be processed via the vessel port by the first and second processing stations or devices. Vessel barrier and lubricity coatings and coated vessels, for example syringes and medical sample collection tubes are disclosed. A vessel processing system is also disclosed.

Claims

1. A syringe comprising:

a barrel and a plunger, the barrel having an inner surface defining a lumen and the plunger having a side surface engaging the barrel inner surface, wherein the inner surface is a substrate comprising a polymer, coated with a barrier coating of SiO_x, in which x is from about 1.5 to about 2.9, and a lubricity layer applied to the barrier coating of SiO_x and configured to provide a lower plunger sliding force or breakout force than the uncoated substrate, the lubricity layer having the following atomic ratios, measured by X-ray photoelectron spectroscopy (XPS),

Si_wO_xC_y,

where w is 1, x in this formula is from about 0.5 to 2.4, and y is from about 0.6 to about 3;

the lubricity layer having a thickness by transmission electron microscopy (TEM) between 10 and 1000 nm;

the lubricity layer deposited by plasma enhanced chemical vapor deposition (PECVD) under conditions effective to form a coating from a precursor comprising a linear siloxane, a monocyclic siloxane, or a combination of any two or more of these precursors.

2. The syringe of claim 1, in which the precursor comprises octamethylcyclotetrasiloxane (OMCTS).

3. The syringe of claim 1, in which the polymer comprises an olefin polymer.

4. The syringe of claim 1, in which the lubricity layer is configured to provide a lower plunger sliding force than the uncoated substrate.

5. The syringe of claim 1, in which the lubricity layer reduces the syringe plunger sliding force moving through the syringe barrel at least 45 percent relative to the uncoated syringe barrel.

6. The syringe of claim 5, in which the plunger sliding force is measured in a Genesis Packaging Automated Syringe Force Tester at a speed of 100 mm/minute, Range=10,000.

7. The syringe of claim 1, in which the lubricity layer reduces the syringe plunger sliding force moving through the syringe barrel at least 60 percent relative to the uncoated syringe barrel.

8. The syringe of claim 1, in which the lubricity layer is configured to provide a lower plunger breakout force than the uncoated substrate.

9. The syringe of claim 1, in which the lubricity layer reduces the syringe plunger breakout force at least 45 percent relative to the uncoated syringe barrel.

10. The syringe of claim 9, in which the syringe plunger breakout force is measured in a Genesis Packaging Automated Syringe Force Tester at a speed of 100 mm/minute, Range=10,000.

11. The syringe of claim 1, in which the lubricity layer reduces the syringe plunger breakout force at least 60 percent relative to the uncoated syringe barrel.

12. The syringe of claim 1, in which the lubricity layer has a density between 1.25 and 1.65 g/cm³ as determined by X-ray reflectivity (XRR).

13. The syringe of claim 1, in which the lubricity layer has an outgas component as determined by gas chromatography/mass spectrometry substantially free of trimethylsilanol.

14. The syringe of claim 1, in which the lubricity layer has an outgas component as determined by gas chromatography/mass spectrometry having at least 10 ng/test of oligomers containing repeating -(Me)2SiO—

moieties, as determined by gas chromatography/mass spectrometry using the following test conditions;

GC Column;

30 m×

0.25 mm DB-5MS (J&

W Scientific), 0.25 μ

m film thickness Flow rate;

1.0 ml/min, constant flow mode Detector;

Mass Selective Detector (MSD) Injection Mode;

Split injection (10;

1 split ratio) Outgassing Conditions;

1 W (37 mm) Chamber, purge for three hour at 85°

C., flow 60 ml/min Oven temperature;

40°

C. (5 min.) to 300°

C. @10°

C./min.;

hold for 5 min, at 300°

C.

15. The syringe of claim 1, in which the lubricity layer has atomic concentrations from 25 to 45% carbon, 25 to 65% silicon, and 10 to 35% oxygen.

16. The syringe of claim 1, in which the lumen has a void volume of from 0.5 to 50 mL.

17. The syringe of claim 1, in which the lubricity layer has a lower wetting tension than the uncoated surface.

18. The syringe of claim 1, in which the lubricity layer has a thickness by transmission electron microscopy (TEM) between 10 and 500 nm.

19. The syringe of claim 1, in which the lubricity layer has atomic concentrations normalized to 100% carbon, oxygen, and silicon, as determined by X-ray photoelectron spectroscopy (XPS), of less than 50% carbon and more than 25% silicon.

20. The syringe of claim 1, in which at least one intervening layer of another material separates the barrier coating and lubricity layer.

21. The syringe of claim 1, in which the lubricity layer is between 100 nm and 500 nm thick.

22. The syringe of claim 1, in which the maximum plunger sliding force of the syringe is between 1.1 lb. (4.9 N) and 2.5 lb. (11.1 N).

23. The syringe of claim 1, in which the maximum plunger sliding force of the syringe is between 1.1 lb. (4.9 N) and 2 lb. (8.9 N).

24. The syringe of claim 1, in which the maximum plunger sliding force of the syringe is between 1.1 lb. (4.9 N) and 1.4 lb. (6.2 N).